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Search for "copper(II)" in Full Text gives 157 result(s) in Beilstein Journal of Organic Chemistry.
Three-component reactions of conjugated dienes, CH acids and formaldehyde under diffusion mixing conditions
- Dmitry E. Shybanov,
- Maxim E. Kukushkin,
- Eugene V. Babaev,
- Nikolai V. Zyk and
- Elena K. Beloglazkina
Beilstein J. Org. Chem. 2025, 21, 262–269, doi:10.3762/bjoc.21.18
- formaldehyde (generated from paraformaldehyde upon heating), an adduct of a methylidene derivative of a CH acid dienophile was detected in some cases only in reference [15] (when carrying out the reaction in a sealed tube in the presence of copper(II) acetate). However, in most reactions only the hetero-Diels
Graphical Abstract
Scheme 1: Knoevenagel and Diels–Alder reactions in the multicomponent synthesis of substituted cyclohexadiene...
Figure 1: Equipment for carrying out reactions by the diffusion mixing method.
Scheme 2: Interaction of diketone 1 with formaldehyde under the diffusion mixing conditions.
Scheme 3: Products of three-component reactions of methylene derivatives, formaldehyde and various dienes.
Scheme 4: Proposed mechanism for the formation of compounds 8 and 9 in the presence of ʟ-proline.
Scheme 5: Interconversion of derivatives 8 and 9.
Scheme 6: Interaction of 4a/4b and 5a/5b mixtures with bromine.
Dioxazolones as electrophilic amide sources in copper-catalyzed and -mediated transformations
- Seungmin Lee,
- Minsuk Kim,
- Hyewon Han and
- Jongwoo Son
Beilstein J. Org. Chem. 2025, 21, 200–216, doi:10.3762/bjoc.21.12
- mixture (E/Z = 1.4:1) of dioxazolones was used. Copper(II)-catalyzed synthesis of 1,2,4-triazole derivatives. Copper(I)-catalyzed synthesis of N-acyl amidines from dioxazolones, acetylenes, and amines. aPerformed under N2 atmosphere. b10 mol % of CuI was used instead of [Cu(OAc)(Xantphos)], with a
Graphical Abstract
Scheme 1: Formation of isocyanates and amidated arenes from dioxazolones.
Scheme 2: Copper-catalyzed synthesis of δ-lactams via open-shell copper nitrenoid transfer. aCuBr (10 mol %) ...
Figure 1: Proposed reaction pathway for the copper-catalyzed synthesis of δ-lactams from dioxazolones.
Scheme 3: Copper(II)-catalyzed synthesis of 1,2,4-triazole derivatives.
Figure 2: Proposed reaction mechanism for the copper-catalyzed synthesis of 1,2,4-triazole analogues from dio...
Scheme 4: Copper(I)-catalyzed synthesis of N-acyl amidines from dioxazolones, acetylenes, and amines. aPerfor...
Figure 3: Proposed reaction mechanism for the copper(I)-catalyzed synthesis of N-acyl amidines.
Scheme 5: Preparation of N-arylamides from dioxazolones and boronic acids using a copper salt.
Figure 4: Proposed reaction pathway for the copper-mediated synthesis of N-arylamides from dioxazolones.
Scheme 6: Copper-catalyzed preparation of N-acyl iminophosphoranes from dioxazolones.
Figure 5: Proposed reaction pathway for the copper-catalyzed synthesis of N-acyl iminophosphoranes from dioxa...
Scheme 7: Copper-catalyzed synthesis of N-acyl sulfenamides. a1.0 equiv of 18 and 2.0 equiv of 19 were used. b...
Figure 6: Proposed reaction mechanism for the copper-catalyzed S-amidation of thiols.
Scheme 8: Copper-catalyzed asymmetric hydroamidation of vinylarenes. a4 mol % + 2 mol % catalyst was used. b4...
Figure 7: Proposed reaction mechanism for the copper-catalyzed hydroamidation of vinylarenes.
Scheme 9: Copper-catalyzed anti-Markovnikov hydroamidation of alkynes.
Figure 8: Proposed reaction mechanism for the copper-catalyzed amidation of alkynes.
Scheme 10: Copper-catalyzed preparation of primary amides through N–O bond reduction using reducing agent.
Figure 9: Proposed catalytic cycle for the copper-catalyzed reduction of dioxazolones.
Cu(OTf)2-catalyzed multicomponent reactions
- Sara Colombo,
- Camilla Loro,
- Egle M. Beccalli,
- Gianluigi Broggini and
- Marta Papis
Beilstein J. Org. Chem. 2025, 21, 122–145, doi:10.3762/bjoc.21.7
- Venezian 21, 20133, Milano, Italy 10.3762/bjoc.21.7 Abstract This review reports the achievements in copper(II) triflate-catalyzed processes concerning the multicomponent reactions, applied to the synthesis of acyclic and cyclic compounds. In particular, for the heteropolycyclic systems mechanistic
- other hand, 4-(α-tetrasubstituted)alkyl-1,2,3-triazoles 45 can be obtained by a two-step reaction of cyclohexanone, amines, silylacetylene, and aryl or alkyl azides in the presence of copper(II) catalysts (Scheme 34) [53]. In a first step, there is the formation of a propargylamine derivative XLIII
- multicomponent synthesis of acyclic and heteropolycyclic systems under copper(II) triflate catalysis are reported. Using alkenes and alkynes as substrates, various types of reactions were considered, including hydroamination, condensation, cross-coupling, C–H functionalization, cycloaddition, aza-Diels–Alder
Graphical Abstract
Figure 1: Plausible general catalytic activation for ionic or radical mechanisms.
Scheme 1: Synthesis of α-aminonitriles 1.
Scheme 2: Synthesis of β-amino ketone or β-amino ester derivatives 3.
Scheme 3: Synthesis of 1-(α-aminoalkyl)-2-naphthol derivatives 4.
Scheme 4: Synthesis of thioaminals 5.
Scheme 5: Synthesis of aryl- or amine-containing alkanes 6 and 7.
Scheme 6: Synthesis of 1-aryl-2-sulfonamidopropanes 8.
Scheme 7: Synthesis of α-substituted propargylamines 10.
Scheme 8: Synthesis of N-propargylcarbamates 11.
Scheme 9: Synthesis of (E)-vinyl sulfones 12.
Scheme 10: Synthesis of o-halo-substituted aryl chalcogenides 13.
Scheme 11: Synthesis of α-aminophosphonates 14.
Scheme 12: Synthesis of unsaturated furanones and pyranones 15–17.
Scheme 13: Synthesis of substituted dihydropyrimidines 18.
Scheme 14: Regioselective synthesis of 1,4-dihydropyridines 20.
Scheme 15: Synthesis of tetrahydropyridines 21.
Scheme 16: Synthesis of furoquinoxalines 22.
Scheme 17: Synthesis of 2,4-substituted quinolines 23.
Scheme 18: Synthesis of cyclic ether-fused tetrahydroquinolines 24.
Scheme 19: Practical route for 1,2-dihydroisoquinolines 25.
Scheme 20: Synthesis of 2,3-dihydroquinazolin-4(1H)-one derivatives 26.
Scheme 21: Synthesis of polysubstituted pyrroles 27.
Scheme 22: Enantioselective synthesis of polysubstituted pyrrolidines 30 directed by the copper complex 29.
Scheme 23: Synthesis of 4,5-dihydropyrazoles 31.
Scheme 24: Synthesis of 2 arylisoindolinones 32.
Scheme 25: Synthesis of imidazo[1,2-a]pyridines 33.
Scheme 26: Synthesis of isoxazole-linked imidazo[1,2-a]azines 35.
Scheme 27: Synthesis of 2,3-dihydro-1,2,4-triazoles 36.
Scheme 28: Synthesis of naphthopyrans 37.
Scheme 29: Synthesis of benzo[g]chromene derivatives 38.
Scheme 30: Synthesis of naphthalene annulated 2-aminothiazoles 39, piperazinyl-thiazoloquinolines 40 and thiaz...
Scheme 31: Synthesis of furo[3,4-b]pyrazolo[4,3-f]quinolinones 42.
Scheme 32: Synthesis of spiroindoline-3,4’-pyrano[3,2-b]pyran-4-ones 43.
Scheme 33: Synthesis of N-(α-alkoxy)alkyl-1,2,3-triazoles 44.
Scheme 34: Synthesis of 4-(α-tetrasubstituted)alkyl-1,2,3-triazoles 45.
Facile one-pot reduction of β-nitrostyrenes to phenethylamines using sodium borohydride and copper(II) chloride
- Laura D’Andrea and
- Simon Jademyr
Beilstein J. Org. Chem. 2025, 21, 39–46, doi:10.3762/bjoc.21.4
- role of the CuCl2 salt is pivotal to the success of this method. Studies on the reduction of CuCl2 by NaBH4 suggest that copper(II) is promptly reduced to free Cu(0), composing up to 96% of the products. The remaining 4% consist of Cu2O and negligible amounts of other copper species [32][33
- ]. Consistently, once the chloride is added, the reduction to free Cu(0) is visually indicated by the immediate disappearance of the blue color of the copper(II) solution, and the formation of a fine suspended black powder. The latter, as metallic copper particles, acts as the actual catalyst. Time plays a
- extraction process and copper(II) removal. However, the addition of DETA led to decreased yields and a deterioration of the phase separation. It was observed that using a 20% aqueous sodium hydroxide solution, instead of 35%, negatively impacted phase separation, making the extraction process more time
Graphical Abstract
Scheme 1: Brief comparison between the main traditional synthetic routes for the preparation of substituted p...
Figure 1: The β-nitrostyrene analogues used in this work.
Scheme 2: Additional products obtained via this method: nitrobenzene and methyl benzoate are reduced in excel...
Figure 2: Numerous masses (m/z) were detected by ESI-MS at T = 0 upon mixing all the reagents to produce 1b.
Figure 3: Structures of proposed adducts. Their masses, 254.2 and 242.2, respectively, were found at T = 0 by...
Scheme 3: Proposed mechanism for the formation of the hydroxylamine side product b. N-Phenethylhydroxylamine (...
Advances in radical peroxidation with hydroperoxides
- Oleg V. Bityukov,
- Pavel Yu. Serdyuchenko,
- Andrey S. Kirillov,
- Gennady I. Nikishin,
- Vera A. Vil’ and
- Alexander O. Terent’ev
Beilstein J. Org. Chem. 2024, 20, 2959–3006, doi:10.3762/bjoc.20.249
- compounds (β-diketones, β-ketoesters, and malonic esters) with TBHP via homogeneous and heterogeneous Cu(II)-catalysis were developed (Scheme 10) [45][46][47]. It was assumed that the reaction pathway includes the formation of diketonate complex A from β-dicarbonyl compound 19 and copper(II) salt, which
- of diphenylacetonitrile (53) with TBHP (Scheme 20) [25]. Peroxide 54 was obtained in a 79% yield using CuBr as the catalyst. The first step of diphenylacetonitrile 53 peroxidation is the oxidation of copper(I) to copper(II) by TBHP, resulting in tert-butoxy radical A, which abstracts the hydrogen
- atom from substrate 53 to form the C-centered radical B. Copper(II) then oxidizes TBHP to form the tert-butylperoxy radical C and copper(I), closing the catalytic copper cycle. tert-Butylperoxy radical C recombines with radical B to yield the product 54. The reaction of a mono-substituted nitrile
Graphical Abstract
Scheme 1: Organic peroxide initiators in polymer chemistry.
Scheme 2: Synthesis of organic peroxides.
Scheme 3: Richness of radical cascades with species formed from hydroperoxides in redox conditions.
Scheme 4: Co-catalyzed allylic peroxidation of alkenes 1 and 3 by TBHP.
Scheme 5: Allylic peroxidation of alkenes 6 by Pd(II)TBHP.
Scheme 6: Cu(I)-catalyzed allylic peroxidation.
Scheme 7: Enantioselective peroxidation of alkenes 10 with TBHP in the presence of copper(I) compounds.
Scheme 8: Oxidation of α-pinene (12) by the Cu(I)/TBHP system.
Scheme 9: Introduction of the tert-butylperoxy fragment into the α-position of cyclic ketones 15 and 17.
Scheme 10: α-Peroxidation of β-dicarbonyl compounds 19 using the Cu(II)/TBHP system.
Scheme 11: Co-catalyzed peroxidation of cyclic compounds 21 with TBHP.
Scheme 12: Co-, Mn- and Fe-catalyzed peroxidation of 2-oxoindoles 23, barbituric acids 25, and 4-hydroxycoumar...
Scheme 13: Cu-catalyzed and metal-free peroxidation of barbituric acid derivatives 31 and 3,4-dihydro-1,4-benz...
Scheme 14: Electrochemical peroxidation of 1,3-dicarbonyl compounds 35.
Scheme 15: Peroxidation of β-dicarbonyl compounds, cyanoacetic esters and malonic esters 37 by the TBAI/TBHP s...
Scheme 16: Cu-catalyzed peroxidation of malonodinitriles and cyanoacetic esters 39 with TBHP.
Scheme 17: Mn-catalyzed remote peroxidation via trifluromethylation of double bond.
Scheme 18: Cu-catalyzed remote peroxidation via trifluromethylthiolation of double bond.
Scheme 19: Fe-, Mn-, and Ru-catalyzed peroxidation of alkylaromatics 45, 47, 49, and 51 with TBHP.
Scheme 20: Cu-catalyzed peroxidation of diphenylacetonitrile (53) with TBHP.
Scheme 21: Cu-catalyzed peroxidation of benzyl cyanides 60 with TBHP.
Scheme 22: Synthesis of tert-butylperoxy esters 63 from benzyl alcohols 62 using the TBAI/TBHP system.
Scheme 23: Enantioselective peroxidation of 2-phenylbutane (64) with TBHP and chiral Cu(I) complex.
Scheme 24: Photochemical synthesis of peroxides 67 from carboxylic acids 66.
Scheme 25: Photochemical peroxidation of benzylic C(sp3)–H.
Scheme 26: Cu- and Ru-catalyzed peroxidation of alkylamines with TBHP.
Scheme 27: Peroxidation of amides 76 with the TBAI/TBHP system.
Scheme 28: Fe-catalyzed functionalization of ethers 78 with TBHP.
Scheme 29: Synthesis of 4-(tert-butylperoxy)-5-phenyloxazol-2(3H)-ones 82 from benzyl alcohols 80 and isocyana...
Scheme 30: Fe- and Co-catalyzed peroxidation of alkanes with TBHP.
Scheme 31: Rh-catalyzed tert-butylperoxy dienone synthesis with TBHP.
Scheme 32: Rh- and Cu-catalyzed phenolic oxidation with TBHP.
Scheme 33: Metal-free peroxidation of phenols 94.
Scheme 34: Cu-catalyzed alkylation–peroxidation of acrylonitrile.
Scheme 35: Cu-catalyzed cycloalkylation–peroxidation of coumarins 99.
Scheme 36: Metal-free cycloalkylation–peroxidation of coumarins 102.
Scheme 37: Difunctionalization of indene 104 with tert-butylperoxy and alkyl groups.
Scheme 38: Acid-catalyzed radical addition of ketones (108, 111) and TBHP to alkenes 107 and acrylates 110.
Scheme 39: Cu-catalyzed alkylation–peroxidation of alkenes 113 with TBHP and diazo compounds 114.
Scheme 40: Cobalt(II)-catalyzed addition of TBHP and 1,3-dicarbonyl compound 116 to alkenes 117.
Scheme 41: Cu(0)- or Co(II)-catalyzed addition of TBHP and alcohols 120 to alkenes 119.
Scheme 42: Fe-catalyzed functionalization of allenes 122 with TBHP.
Scheme 43: Fe-catalyzed alkylation–peroxidation of alkenes 125 and 127.
Scheme 44: Fe- and Co-catalyzed alkylation–peroxidation of alkenes 130, 133 and 134 with TBHP and aldehydes as...
Scheme 45: Carbonylation–peroxidation of alkenes 137, 140, 143 with hydroperoxides and aldehydes.
Scheme 46: Carbamoylation–peroxidation of alkenes 146 with formamides and TBHP.
Scheme 47: TBAB-catalyzed carbonylation–peroxidation of alkenes.
Scheme 48: VOCl2-catalyzed carbonylation–peroxidation of alkenes 152.
Scheme 49: Acylation–peroxidation of alkenes 155 with aldehydes 156 and TBHP using photocatalysis.
Scheme 50: Cu-catalyzed peroxidation of styrenes 158.
Scheme 51: Fe-catalyzed acylation-peroxidation of alkenes 161 with carbazates 160 and TBHP.
Scheme 52: Difunctionalization of alkenes 163, 166 with TBHP and (per)fluoroalkyl halides.
Scheme 53: Difunctionalization of alkenes 169 and 172 with hydroperoxides and sodium (per)fluoromethyl sulfina...
Scheme 54: Trifluoromethylation–peroxidation of styrenes 175 using MOF Cu3(BTC)2 as a catalyst.
Scheme 55: Difunctionalization of alkenes 178 with tert-butylperoxy and dihalomethyl fragments.
Scheme 56: Difunctionalization of alkenes 180 with the tert-butylperoxy and dihalomethyl moieties.
Scheme 57: The nitration–peroxidation of alkenes 182 with t-BuONO and TBHP.
Scheme 58: Azidation–peroxidation of alkenes 184 with TMSN3 and TBHP.
Scheme 59: Co-catalyzed bisperoxidation of butadiene 186.
Scheme 60: Bisperoxidation of styrene (189) and acrylonitrile (192) with TBHP by Minisci.
Scheme 61: Mn-catalyzed synthesis of bis(tert-butyl)peroxides 195 from styrenes 194.
Scheme 62: Bisperoxidation of arylidene-9H-fluorenes 196 and 3-arylidene-2-oxoindoles 198 with TBHP under Mn-c...
Scheme 63: Synthesis of bisperoxides from styrenes 200 and 203 using the Ru and Rh catalysis.
Scheme 64: Iodine-catalyzed bisperoxidation of styrenes 206.
Scheme 65: Synthesis of di-tert-butylperoxyoxoindoles 210 from acrylic acid anilides 209 using a Pd(II)/TBHP o...
Scheme 66: Pinolation/peroxidation of styrenes 211 catalyzed by Cu(I).
Scheme 67: TBAI-catalyzed acyloxylation–peroxidation of alkenes 214 with carboxylic acids and TBHP.
Scheme 68: Difunctionalization of alkenes 217 with TBHP and water or alcohols.
Scheme 69: TBAI-catalyzed hydroxyperoxidation of 1,3-dienes 220.
Scheme 70: Hydroxyperoxidation of 1,3-dienes 220.
Scheme 71: Iodination/peroxidation of alkenes 223 with I2 and hydroperoxides.
Scheme 72: The reactions of cyclic enol ethers 226 and 228 with I2/ROOH system.
Scheme 73: Synthesis of 1-(tert-butylperoxy)-2-iodoethanes 231.
Scheme 74: Synthesis of 1-iodo-2-(tert-butylperoxy)ethanes 233.
Scheme 75: Cu-catalyzed phosphorylation–peroxidation of alkenes 234.
Scheme 76: Co-catalyzed phosphorylation–peroxidation of alkenes 237.
Scheme 77: Ag-catalyzed sulfonylation–peroxidation of alkenes 241.
Scheme 78: Co-catalyzed sulfonylation–peroxidation of alkenes 244.
Scheme 79: Synthesis of α/β-peroxysulfides 248 and 249 from styrenes 247.
Scheme 80: Cu-catalyzed trifluoromethylthiolation–peroxidation of alkenes 250 and allenes 252.
Scheme 81: Photocatalytic sulfonyl peroxidation of alkenes 254 via deamination of N-sulfonyl ketimines 255.
Scheme 82: Photoredox-catalyzed 1,4-peroxidation–sulfonylation of enynones 257.
Scheme 83: Cu-catalyzed silylperoxidation of α,β-unsaturated compounds 260 and enynes 261.
Scheme 84: Fe-catalyzed silyl peroxidation of alkenes.
Scheme 85: Cu-catalyzed germyl peroxidation of alkenes 267.
Scheme 86: TBAI-catalyzed intramolecular cyclization of diazo compounds 269 with further peroxidation.
Scheme 87: Co-catalyzed three-component coupling of benzamides 271, diazo compounds 272 and TBHP.
Scheme 88: Co-catalyzed esterification-peroxidation of diazo compounds 274 with TBHP and carboxylic acids 275.
Scheme 89: Cu-catalyzed alkylation–peroxidation of α-carbonylimines 277 or ketones 280.
Scheme 90: Mn-catalyzed ring-opening peroxidation of cyclobutanols 282 with TBHP.
Scheme 91: Peroxycyclization of tryptamines 284 with TBHP.
Scheme 92: Radical cyclization–peroxidation of homotryptamines 287.
Scheme 93: Iodine-catalyzed oxidative coupling of indoles 288, cyanoacetic esters and TBHP.
Scheme 94: Summary of metal-catalyzed peroxidation processes.
Investigation of a bimetallic terbium(III)/copper(II) chemosensor for the detection of aqueous hydrogen sulfide
- Parvathy Mini,
- Michael R. Grace,
- Genevieve H. Dennison and
- Kellie L. Tuck
Beilstein J. Org. Chem. 2024, 20, 2818–2826, doi:10.3762/bjoc.20.237
- /bjoc.20.237 Abstract The chemosensor properties of a bimetallic terbium(III)/copper(II) complex functionalized with a 4-(2-pyridyl)-1,2,3-triazole ligand for the detection of Cu2+ ions and, aqueous and gaseous hydrogen sulfide was investigated. The 4-(2-pyridyl)-1,2,3-triazole ligand functions both as
- of detection for aqueous hydrogen sulfide was 0.63 μM (20 ppb). No luminescent changes of the bimetallic terbium(III)/copper(II) complex were observed in the presence of gaseous hydrogen sulfide, and thus this sensor can only be used for the detection of aqueous hydrogen sulfide. Keywords
- , highly sensitive chemosensors via a facile synthetic route/method, we have explored three chelates for lanthanide ions (DO3A, 2,6-pyridinedicarboxylic acid and DO2A), resulting in complexes with different overall charges. Additionally we have explored two copper(II) binding groups (di(2-picolyl)amine and
Graphical Abstract
Figure 1: Previously reported lanthanide complexes [12,16,17].
Scheme 1: Synthesis of Tb.1.
Figure 2: Absorption (red line), excitation (yellow line, λem = 615 nm), and emission (green line, λex = 250 ...
Figure 3: (a) Changes in the luminescence emission spectrum of 5 µM [Tb.1·3Cu]3+ upon the addition of Na2S (0...
Figure 4: (a) Changes in the luminescence emission spectrum of 5 µM [Tb.1·3Cu]3+ upon the addition of Na2S (0...
Figure 5: Luminescence intensity of 5 μM Tb.1 in 10 mM Tris-HCl buffer, pH 7.4, containing 5% DMSO upon the a...
Figure 6: Changes in luminescent intensity of [Tb.1·3Cu]3+ (5 µM) detected at 545 nm in the presence of vario...
Figure 7: Chemical structure and mode of action of [Tb(DPA-N3)3]3− for detection of H2S(g) [11].
Synthesis, electrochemical properties, and antioxidant activity of sterically hindered catechols with 1,3,4-oxadiazole, 1,2,4-triazole, thiazole or pyridine fragments
- Daria A. Burmistrova,
- Andrey Galustyan,
- Nadezhda P. Pomortseva,
- Kristina D. Pashaeva,
- Maxim V. Arsenyev,
- Oleg P. Demidov,
- Mikhail A. Kiskin,
- Andrey I. Poddel’sky,
- Nadezhda T. Berberova and
- Ivan V. Smolyaninov
Beilstein J. Org. Chem. 2024, 20, 2378–2391, doi:10.3762/bjoc.20.202
- action of a soft oxidant a bis-(neo-cuproine) copper(II) complex. The CUPRACTEAC parameter varies in a wide range of values from 0.12 to 1.92 (Table 2). Compounds 1 and 2 containing a 1,3,4-oxadiazole ring and a sulfur atom directly bonded to the catechol ring are practically inactive in this reaction
Graphical Abstract
Scheme 1: Synthesis of catechol-containing compounds 1–9.
Figure 1: The X-ray structure of catechol 5 (the thermal ellipsoids of 50% probability). The hydrogen atoms e...
Figure 2: The X-ray structures of catechols 6 (a) and 8 (b) (the thermal ellipsoids of 50% probability). The ...
Figure 3: Fragment of the pack of catechol 5 in crystal (the H-bonds and π–π interactions are shown as dotted...
Figure 4: The interactions in pair of independent molecules A and B of 6 in crystal 6·0.5CH3CN (the H-bonds a...
Figure 5: Fragment of the pack of catechol 8 in crystal (the H-bonds and π–π interactions are shown as dotted...
Scheme 2: Electrochemical transformations of compounds 1–3.
Figure 6: The CV curve of 2 at the potential range from −0.50 to 1.60 V (CH3CN, GC electrode, Ag/AgCl/KCl(sat...
Figure 7: The CV curves of 3 at the potential ranges from –0.5 to 1.2 V (curve 1); from –0.5 to 2.0 V (curve ...
Figure 8: The CV curves of 7 at the potential ranges from –0.5 to 1.3 V (curve 1); from –0.5 to 1.8 V (curve ...
Scheme 3: Proposed mechanism of an electrooxidation of compounds 6–8.
Figure 9: The level of TBARS in rat liver homogenates in vitro, in the presence of compounds 1–9, Trolox, and...
Multicomponent syntheses of pyrazoles via (3 + 2)-cyclocondensation and (3 + 2)-cycloaddition key steps
- Ignaz Betcke,
- Alissa C. Götzinger,
- Maryna M. Kornet and
- Thomas J. J. Müller
Beilstein J. Org. Chem. 2024, 20, 2024–2077, doi:10.3762/bjoc.20.178
Graphical Abstract
Scheme 1: Consecutive three-component synthesis of pyrazoles 1 via in situ-formed 1,3-diketones 2 [44].
Scheme 2: Consecutive three-component synthesis of 4-ethoxycarbonylpyrazoles 5 via SmCl3-catalyzed acylation ...
Scheme 3: Consecutive four-component synthesis of 1-(thiazol-2-yl)pyrazole-3-carboxylates 8 [51].
Scheme 4: Three-component synthesis of thiazolylpyrazoles 17 via in situ formation of acetoacetylcoumarins 18 ...
Scheme 5: Consecutive pseudo-four-component and four-component synthesis of pyrazoles 21 from sodium acetylac...
Scheme 6: Consecutive three-component synthesis of 1-substituted pyrazoles 24 from boronic acids, di(Boc)diim...
Scheme 7: Consecutive three-component synthesis of N-arylpyrazoles 25 via in situ formation of aryl-di(Boc)hy...
Scheme 8: Consecutive three-component synthesis of 1,3,4-substituted pyrazoles 27 and 28 from methylhydrazine...
Scheme 9: Consecutive three-component synthesis of 4-allylpyrazoles 32 via oxidative allylation of 1,3-dicarb...
Scheme 10: Pseudo-five-component synthesis of tris(pyrazolyl)methanes 35 [61].
Scheme 11: Pseudo-three-component synthesis of 5-(indol-3-yl)pyrazoles 39 from 1,3,5-triketones 38 [64].
Scheme 12: Three-component synthesis of thiazolylpyrazoles 43 [65].
Scheme 13: Three-component synthesis of triazolo[3,4-b]-1,3,4-thiadiazin-3-yl substituted 5-aminopyrazoles 47 [67]....
Scheme 14: Consecutive three-component synthesis of 5-aminopyrazoles 49 via formation of β-oxothioamides 50 [68].
Scheme 15: Synthesis of 3,4-biarylpyrazoles 52 from aryl halides, α-bromocinnamaldehyde, and tosylhydrazine vi...
Scheme 16: Consecutive three-component synthesis of 3,4-substituted pyrazoles 57 from iodochromones 55 by Suzu...
Scheme 17: Pseudo-four-component synthesis of pyrazolyl-2-pyrazolines 59 by ring opening/ring closing cyclocon...
Scheme 18: Consecutive three-component synthesis of pyrazoles 61 [77].
Scheme 19: Three-component synthesis of pyrazoles 62 from malononitrile, aldehydes, and hydrazines [78-90].
Scheme 20: Four-component synthesis of pyrano[2,3-c]pyrazoles 63 [91].
Scheme 21: Three-component synthesis of persubstituted pyrazoles 65 from aldehydes, β-ketoesters, and hydrazin...
Scheme 22: Three-component synthesis of pyrazol-4-carbodithioates 67 [100].
Scheme 23: Regioselective three-component synthesis of persubstituted pyrazoles 68 catalyzed by ionic liquid [...
Scheme 24: Consecutive three-component synthesis of 4-halopyrazoles 69 and anellated pyrazoles 70 [102].
Scheme 25: Three-component synthesis of 2,2,2-trifluoroethyl pyrazole-5-carboxylates 72 [103].
Scheme 26: Synthesis of pyrazoles 75 in a one-pot process via carbonylative Heck coupling and subsequent cycli...
Scheme 27: Copper-catalyzed three-component synthesis of 1,3-substituted pyrazoles 76 [105].
Scheme 28: Pseudo-three-component synthesis of bis(pyrazolyl)methanes 78 by ring opening-ring closing cyclocon...
Scheme 29: Three-component synthesis of 1,4,5-substituted pyrazoles 80 [107].
Scheme 30: Consecutive three-component synthesis of 3,5-bis(fluoroalkyl)pyrazoles 83 [111].
Scheme 31: Consecutive three-component synthesis of difluoromethanesulfonyl-functionalized pyrazole 88 [114].
Scheme 32: Consecutive three-component synthesis of perfluoroalkyl-substituted fluoropyrazoles 91 [115].
Scheme 33: Regioselective consecutive three-component synthesis of 1,3,5-substituted pyrazoles 93 [116].
Scheme 34: Three-component synthesis of pyrazoles 96 mediated by trimethyl phosphite [117].
Scheme 35: One-pot synthesis of pyrazoles 99 via Liebeskind–Srogl cross-coupling/cyclocondensation [118].
Scheme 36: Synthesis of 1,3,5-substituted pyrazoles 101 via domino condensation/Suzuki–Miyaura cross-coupling ...
Scheme 37: Consecutive three-component synthesis of 1,3,5-trisubstituted pyrazoles 102 and 103 by Sonogashira ...
Scheme 38: Polymer analogous consecutive three-component synthesis of pyrazole-based polymers 107 [132].
Scheme 39: Synthesis of 1,3,5-substituted pyrazoles 108 by sequentially Pd-catalyzed Kumada–Sonogashira cycloc...
Scheme 40: Consecutive four-step one-pot synthesis of 1,3,4,5-substituted pyrazoles 110 [137].
Scheme 41: Four-component synthesis of pyrazoles 113, 115, and 117 via Sonogashira coupling and subsequent Suz...
Scheme 42: Consecutive four- or five-component synthesis for the preparation of 4-pyrazoly-1,2,3-triazoles 119...
Scheme 43: Four-component synthesis of pyrazoles 121 via alkynone formation by carbonylative Pd-catalyzed coup...
Scheme 44: Preparation of 3-azulenyl pyrazoles 124 by glyoxylation, decarbonylative Sonogashira coupling, and ...
Scheme 45: Four-component synthesis of a 3-indoloylpyrazole 128 [147].
Scheme 46: Two-step synthesis of 5-acylpyrazoles 132 via glyoxylation-Stephen–Castro sequence and subsequent c...
Scheme 47: Copper on iron mediated consecutive three-component synthesis of 3,5-substituted pyrazoles 136 [150].
Scheme 48: Consecutive three-component synthesis of 3-substituted pyrazoles 141 by Sonogashira coupling and su...
Scheme 49: Consecutive three-component synthesis of pyrazoles 143 initiated by Cu(I)-catalyzed carboxylation o...
Scheme 50: Consecutive three-component synthesis of benzamide-substituted pyrazoles 146 starting from N-phthal...
Scheme 51: Consecutive three-component synthesis of 1,3,5-substituted pyrazoles 148 [156].
Scheme 52: Three-component synthesis of 4-ninhydrin-substituted pyrazoles 151 [158].
Scheme 53: Consecutive four-component synthesis of 4-(oxoindol)-1-phenylpyrazole-3-carboxylates 155 [159].
Scheme 54: Three-component synthesis of pyrazoles 160 [160].
Scheme 55: Consecutive three-component synthesis of pyrazoles 165 [162].
Scheme 56: Consecutive three-component synthesis of 3,5-disubstituted and 3-substituted pyrazoles 168 and 169 ...
Scheme 57: Three-component synthesis of 3,4,5-substituted pyrazoles 171 via 1,3-dipolar cycloaddition of vinyl...
Scheme 58: Three-component synthesis of pyrazoles 173 and 174 from aldehydes, tosylhydrazine, and vinylidene c...
Scheme 59: Three-component synthesis of pyrazoles 175 from glyoxyl hydrates, tosylhydrazine, and electron-defi...
Scheme 60: Pseudo-four-component synthesis of pyrazoles 177 from glyoxyl hydrates, tosylhydrazine, and aldehyd...
Scheme 61: Consecutive three-component synthesis of pyrazoles 179 via Knoevenagel-cycloaddition sequence [179].
Scheme 62: Three-component synthesis of 5-dimethylphosphonate substituted pyrazoles 182 from aldehydes, the Be...
Scheme 63: Consecutive three-component synthesis of 5-(dimethyl phosphonate)-substituted pyrazoles 185 from al...
Scheme 64: Three-component synthesis of 5-(dimethyl phosphonate)-substituted pyrazoles 187 from aldehydes, the...
Scheme 65: Three-component synthesis of 5-diethylphosphonate/5-phenylsulfonyl substituted pyrazoles 189 from a...
Scheme 66: Pseudo-three-component synthesis of 3-(dimethyl phosphonate)-substituted pyrazoles 190 [185].
Scheme 67: Three-component synthesis of 3-trifluoromethylpyrazoles 193 [186].
Scheme 68: Consecutive three-component synthesis of 5-stannyl-substituted 4-fluoropyrazole 197 [191,192].
Scheme 69: Pseudo-three-component synthesis of 3,5-diacyl-4-arylpyrazoles 199 [195].
Scheme 70: Three-component synthesis of pyrazoles 204 via nitrilimines [196].
Scheme 71: Three-component synthesis of 1,3,5-substituted pyrazoles 206 via formation of nitrilimines and sali...
Scheme 72: Pseudo four-component synthesis of pyrazoles 209 from acetylene dicarboxylates 147, hydrazonyl chlo...
Scheme 73: Consecutive three-component synthesis of pyrazoles 213 via syndnones 214 [200].
Scheme 74: Consecutive three-component synthesis of pyrazoles 216 via in situ-formed diazomethinimines 217 [201].
Scheme 75: Consecutive three-component synthesis of 3-methylthiopyrazoles 219 from aldehydes, hydrazine, and 1...
Scheme 76: Three-component synthesis of 1,3,5-substituted pyrazoles 220 from aldehydes, hydrazines, and termin...
Scheme 77: Three-component synthesis of 1,3,4,5-substituted pyrazoles 222 from aldehydes, hydrazines, and DMAD ...
Scheme 78: Pseudo three-component synthesis of pyrazoles 224 from sulfonyl hydrazone and benzyl acrylate under...
Scheme 79: Titanium-catalyzed consecutive four-component synthesis of pyrazoles 225 via enamino imines 226 [211]. a...
Scheme 80: Titanium-catalyzed three-component synthesis of pyrazoles 227 via enhydrazino imine complex interme...
Scheme 81: Pseudo-three-component synthesis of pyrazoles 229 via Glaser coupling of terminal alkynes and photo...
Scheme 82: Copper(II)acetate-mediated three-component synthesis of pyrazoles 232 [216].
Scheme 83: Copper-catalyzed three-component synthesis of 1,3,4-substituted pyrazole 234 from oxime acetates, a...
Scheme 84: Three-component synthesis of 3-trifluoroethylpyrazoles 239 [218].
Scheme 85: Pseudo-three-component synthesis of 1,4-bisulfonyl-substituted pyrazoles 242 [219].
Scheme 86: Three-component synthesis of 4-hydroxypyrazole 246 [221].
Diameter-selective extraction of single-walled carbon nanotubes by interlocking with Cu-tethered square nanobrackets
- Guoqing Cheng and
- Naoki Komatsu
Beilstein J. Org. Chem. 2024, 20, 1298–1307, doi:10.3762/bjoc.20.113
- -TOF mass spectra. Upon extraction of SWNTs with the nanobracket and copper(II), in situ-formed square Cu-nanobrackets are found to interlock SWNTs to disperse them in 2-propanol. The interlocking is confirmed by Raman spectroscopy after thorough washing of the extracted SWNTs. Pristine SWNTs were
- chromatographic purification due to much lower solubility of 4b compared to 4a. The metal complex of 4b with copper(II) was prepared, because copper(II) exhibited better extraction and separation abilities than cobalt(II) and palladium(II) in the case of Cu-tethered rectangular nanobrackets 1a [11]. Before SWNT
- extraction, the square Cu-nanobrackets 1b were successfully obtained by the reaction between the nanobracket 4b and copper(II) acetylacetonate in THF at room temperature. The product was characterized as 1b by MALDI-TOF mass spectrometry (Figure 1a), absorption (Figure 1b) and Raman (Figure 2c
Graphical Abstract
Scheme 1: Chemical structures of Cu-tethered tetragonal nanobrackets 1a and 1b.
Scheme 2: Synthesis of nanobracket 4. Reaction conditions: i) XPhos Pd G2, XPhos, B2(OH)4, KOAc, EtOH, 80 °C,...
Figure 1: (a) MALDI-TOF mass spectrum of Cu-nanobrackets 1b, where the inset shows the isotope peaks of [1b]+...
Figure 2: DFT-optimized structure of Cu-nanobrackets (a) 1a and (b) 1b. The yellow regions indicate their sph...
Figure 3: (a) Absorption spectra of Cu-nanobrackets 1b and SWNT extract; (b) Raman spectra of Cu-nanobrackets ...
Figure 4: Raman spectra of HiPco SWNTs, e-, i-, and p-SWNTs (λex = 488 nm) at RBM and G-band regions. Raman i...
Figure 5: (a) Raman spectra of HiPco and extracted SWNTs at 488, 633 and 785 nm excitation wavelengths, norma...
Figure 6: (a) Binding energy between SWNTs of various (n,m)-structures with Cu-nanobrackets 1a and 1b; GFN2-x...
Evaluation of the enantioselectivity of new chiral ligands based on imidazolidin-4-one derivatives
- Jan Bartáček,
- Karel Chlumský,
- Jan Mrkvička,
- Lucie Paloušová,
- Miloš Sedlák and
- Pavel Drabina
Beilstein J. Org. Chem. 2024, 20, 684–691, doi:10.3762/bjoc.20.62
- based on derivatives of imidazolidin-4-one were synthesised and characterised. The catalytic activity and enantioselectivity of their corresponding copper(II) complexes were studied in asymmetric Henry reactions. It was found that the enantioselectivity of these catalysts is overall very high and
- -(pyridin-2-yl)imidazolidin-4-one, differentiated by various substitutions at the imidazolidine ring [5][6][7]. Their copper(II) complexes were evaluated as efficient enantioselective catalysts, particularly in asymmetric Henry reactions (Scheme 1). Subsequent research has led to the development of various
- chiral metal complex catalyst but also as an enantioselective organocatalyst [17]. Accordingly, its application in enantioselective organocatalysis, particularly in asymmetric reactions through “enamine activation”, warrants further investigation. Results and Discussion The corresponding copper(II
Graphical Abstract
Scheme 1: The preparation of 5-isopropyl-5-methyl-2-(pyridin-2-yl)imidazolidin-4-one derivatives and their ap...
Figure 1: The structure of newly designed ligands I–IV.
Figure 2: Plausible transition structures for the Henry reaction.
Switchable molecular tweezers: design and applications
- Pablo Msellem,
- Maksym Dekthiarenko,
- Nihal Hadj Seyd and
- Guillaume Vives
Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45
- regulated guest binding. Other groups developed coordination-switchable molecular tweezers with several ligands based on nitrogen coordination sites. Plante and Glass reported tweezers 23 using a bisimidazole-pyridine unit with anisole arms (Figure 14a) [55]. This system can coordinate copper(II) in a
- bipyridine-based molecular tweezers 30 (Figure 16b) with corannulene recognition units on positions 4 and 4’ (open-by-default) for fullerene complexation [63]. The bipyridine can be switched from s-trans to s-cis-conformation by the addition of copper(II) and one equivalent of 1,2-bis(diphenylphosphino
Graphical Abstract
Figure 1: Principle of switchable molecular tweezers.
Figure 2: Principle of pH-switchable molecular tweezers 1 [19].
Figure 3: a) pH-Switchable tweezers 2 substituted with alkyl chains as switchable lipids. b) Schematic depict...
Figure 4: Modification of spectral properties of 3 by controlled induction of Pt–Pt interactions.
Figure 5: Conformational switching of di(hydroxyphenyl)pyrimidine-based tweezer 4 upon alkylation or fluoride...
Figure 6: Hydrazone-based pH-responsive tweezers 5 for mesogenic modulation.
Figure 7: pH-Switchable molecular tweezers 6 bearing acridinium moieties.
Figure 8: a) Terpyridine and pyridine-hydrazone-pyridine analogs molecular tweezers and b) extended pyridine ...
Figure 9: Terpyridine-based molecular tweezers with M–salphen arms and their field of application. Figure 9 was adapt...
Figure 10: a) Terpyridine-based molecular tweezers for diphosphate recognition [48]; b) bishelicene chiroptical te...
Figure 11: Terpyridine-based molecular tweezers with allosteric cooperative binding.
Figure 12: Terpyridine-based molecular tweezers presenting closed by default conformation.
Figure 13: Pyridine-pyrimidine-pyridine-based molecular tweezers.
Figure 14: Coordination-responsive molecular tweezers based on nitrogen-containing ligands.
Figure 15: Molecular tweezers exploiting the remote bipyridine or pyridine binding to trigger the conformation...
Figure 16: Bipyridine-based molecular tweezers exploiting the direct s-trans to s-cis-switching for a) anion b...
Figure 17: a) Podand-based molecular tweezers [66,67]. b) Application of tweezers 32 for the catalytic allosteric reg...
Figure 18: Anion-triggered molecular tweezers based on calix[4]pyrrole.
Figure 19: Anion-triggered molecular tweezers.
Figure 20: a) Principle of the weak link approach (WLA) developed by Mirkin and its application to b) symmetri...
Figure 21: Molecular tweezers as allosteric catalyst in asymmetric epoxide opening [80].
Figure 22: Allosteric regulation of catalytic activity in ring-opening polymerization with double tweezers 41.
Figure 23: a) Conformational switching of 42 by intramolecular –S–S– bridge formation. b) Shift of conformatio...
Figure 24: a) Redox-active glycoluril-TTF tweezers 44. b) Mechanism of stepwise oxidation of said tweezers wit...
Figure 25: Mechanism of formation of the mixed-valence dimers of tweezers 45.
Figure 26: Mechanism of carbohydrate liberation upon redox-mediated conformation switching of 46.
Figure 27: a) The encapsulation properties of 47 as well as the DCTNF release process from its host–guest comp...
Figure 28: Redox-active bipyridinium-based tweezers. a) With a ferrocenyl hinge 49, b) with a propyl hinge 50 ...
Figure 29: Redox-active calix[4]arene porphyrin molecular tweezers.
Figure 30: a) Mechanism of the three orthogonal stimuli. b) Cubic scheme showing the eight different states of ...
Figure 31: Redox-controlled molecular gripper based on a diquinone resorcin[4]arene.
Figure 32: a) Shinkai's butterfly tweezers and their different host–guest properties depending on the isomer. ...
Figure 33: Cyclam-tethered tweezers and their different host–guest complexes depending on their configuration.
Figure 34: Azobenzene-based catalytic tweezers.
Figure 35: Photoswitchable PIEZO channel mimic.
Figure 36: Stilbene-based porphyrin tweezers for fullerene recognition.
Figure 37: Stiff-stilbene-based tweezers with urea or thiourea functional units for a) anion binding, b) anion...
Figure 38: Feringa’s photoswitchable organocatalyst (a) and different catalyzed reactions with that system (b)....
Figure 39: a) Irie and Takeshita’s thioindigo-based molecular tweezers. b) Family of hemithioindigo-based mole...
Figure 40: Dithienylethylene crown ether-bearing molecular tweezers reported by Irie and co-workers.
Catalytic multi-step domino and one-pot reactions
- Svetlana B. Tsogoeva
Beilstein J. Org. Chem. 2024, 20, 254–256, doi:10.3762/bjoc.20.25
- -aminopyrazoles with azlactones under solvent-free conditions, through subsequent elimination of a benzamide molecule in a superbasic medium, is described by the Fisyuk group [13]. A further facile one-pot process toward a new series of copper(II) benzo[f]chromeno[2,3-h]quinoxalinoporphyrin analogues is described
Figure 1: Comparison of a classical “stop-and-go” synthesis with a domino reaction.
Aldiminium and 1,2,3-triazolium dithiocarboxylate zwitterions derived from cyclic (alkyl)(amino) and mesoionic carbenes
- Nedra Touj,
- François Mazars,
- Guillermo Zaragoza and
- Lionel Delaude
Beilstein J. Org. Chem. 2023, 19, 1947–1956, doi:10.3762/bjoc.19.145
- ). The active catalytic species for the CuAAC reaction were generated by reducing copper(II) sulfate with sodium ascorbate according to literature procedures [66][67]. 2-Azido-1,3,5-trimethylbenzene (mesityl azide) was easily synthesized in a distinct, preliminary step through the Sandmeyer reaction of
Graphical Abstract
Figure 1: Various types of stable singlet carbenes and their acronyms.
Figure 2: Various types of NHC·CS2 zwitterions and their coordination modes.
Scheme 1: Synthesis of CAAC·CS2 zwitterion 2 from its free carbene parent 1.
Scheme 2: Synthesis of CAAC·CS2 zwitterions 4a–c with KN(SiMe3)2.
Scheme 3: Synthesis of 1,2,3-triazolium iodides 5a–f.
Scheme 4: Synthesis of MIC·CS2 zwitterions 6a and 6b with KN(SiMe3)2.
Scheme 5: Synthesis of MIC·CS2 zwitterions 6c–f with NaOt-Bu.
Figure 3: ORTEP representations of zwitterions 4a (CAAC-Mes-Cy·CS2, top) and 4c (CAAC-Die-MePh·CS2, bottom) w...
Figure 4: ORTEP representations of zwitterions 6b (MIC-Dip-Ph-Me·CS2, top) and 6e (MIC-Mes-Bu-Me·CS2, bottom)...
Effects of the aldehyde-derived ring substituent on the properties of two new bioinspired trimethoxybenzoylhydrazones: methyl vs nitro groups
- Dayanne Martins,
- Roberta Lamosa,
- Talis Uelisson da Silva,
- Carolina B. P. Ligiero,
- Sérgio de Paula Machado,
- Daphne S. Cukierman and
- Nicolás A. Rey
Beilstein J. Org. Chem. 2023, 19, 1713–1727, doi:10.3762/bjoc.19.125
- affect its pharmacological properties and metallophoric potential against copper(II) when compared to the unsubstituted counterpart. Nevertheless, the bioinspired compound was still able to reduce oxidative stress and affect the aggregation of the amyloid-β peptide, related to pathophysiological events
Graphical Abstract
Scheme 1: Structure of (A) 3-methylsalicylaldehyde 3,4,5-trimethoxybenzoyl hydrazone (hdz-CH3) and (B) 3-nitr...
Figure 1: ORTEP representation of the new N-acylhydrazones synthesized in the present work, drawn with therma...
Figure 2: (A) Superposition of molecular structures and stacked motifs of (B) hdz-CH3 and (C) hdz-NO2.
Figure 3: Overlap of the experimental (carbon atoms colored in gray) and theoretical structures (calculated w...
Figure 4: Mid-infrared spectra of the compounds. Experimental conditions: KBr pellets, room temperature. Calc...
Figure 5: 1H NMR (400 MHz) spectra of (A) hdz-CH3 and (B) hdz-NO2 in DMSO-d6 at 25 °C.
Figure 6: Electronic absorption spectra in a selected wavelength region for a solution of hdz-CH3 in 10% DMSO...
Figure 7: Electronic absorption spectra of hdz-NO2 in selected wavelength regions. Experimental conditions: l...
Scheme 2: General scheme for the synthesis of the studied hydrazones.
Tying a knot between crown ethers and porphyrins
- Maksym Matviyishyn and
- Bartosz Szyszko
Beilstein J. Org. Chem. 2023, 19, 1630–1650, doi:10.3762/bjoc.19.120
- of coordination compounds of copper(II), iron(II/III), manganese(II), nickel(II), and cobalt(II) with 9-Zn and 9-Cu was demonstrated. The emission quenching was rationalised considering the binding of the transition metal within the crown ether cavity. No quenching was observed upon the addition of
- porphyrins was investigated, resulting in the formation of lead(II), zinc(II), and copper(II) binuclear coordination compounds [54]. The synthetic methodology developed by Sessler allowed to generate a variety of expanded Schiff porphyrinoids [30][128] and texaphyrins [57][60][129]. The group has also
- the aryl group at the meso-position of the dipyrrin moiety. Compound 40 was tested for sensing metal ions, and while no significant changes were observed with most cations, the addition of Cu(II) resulted in a colour change. UV–vis spectroscopy and mass spectrometry confirmed the 1:1 copper(II
Graphical Abstract
Figure 1: Porphyrin and crown ether.
Figure 2: Timeline demonstrating the contributions into the crown ether–porphyrin chemistry.
Figure 3: Tetra-crowned porphyrin 1 and dimer 2 formed upon K+ binding.
Figure 4: meso-Crowned 25-oxasmaragdyrins 3a–c and their boron(III) complexes (3a–c)-BF2.
Scheme 1: CsF ion-pair binding of 4. The molecular structure of 4-CsF is shown on the right [101].
Figure 5: CsF ion pair binding by 5. The molecular structure of 5-CsF is shown on the right [102].
Scheme 2: Ion-pair binding by 6. The molecular structure of (6-CsCl)2 is shown on the right [103].
Scheme 3: Hydrated fluoride binding by 7 [104].
Figure 6: β-Crowned porphyrin 8.
Figure 7: Crown ether-capped porphyrins 9.
Figure 8: The capped porphyrin 10 and complex [10-PQ](PF6)2.
Figure 9: The double-capped porphyrin 11.
Figure 10: Selected examples of iminoporphyrinoids [58,122].
Scheme 4: The synthesis of 13.
Scheme 5: Tripyrrane-based crown ether-embedding porphyrinoid 15.
Figure 11: Macrocycles 16–19 and their coordination compounds.
Scheme 6: The flexibility of 16-Co [66].
Figure 12: Hexagonal wheel composed of six 16-Co(III) monomers [66].
Scheme 7: The synthesis of 16-V [67].
Figure 13: The molecular structure of dimers [16-Mn]2 [67].
Scheme 8: Synthesis of crownphyrins 28–33. Compounds 23a/b and 29a/b were obtained from 4,7,10-trioxa-1,13-tr...
Figure 14: The molecular structures of 22a, 34a·(HCl)2, and 29b [69].
Figure 15: Molecular structures of 22a-Pb and (29b)2-Zn [69].
Scheme 9: Reactivity of 29a/b.
Scheme 10: Synthesis of 36 and 37 [131].
Scheme 11: Synthesis of 40–45.
Figure 16: Potential applications of porphyrin-crown ether hybrids.
N-Sulfenylsuccinimide/phthalimide: an alternative sulfenylating reagent in organic transformations
- Fatemeh Doraghi,
- Seyedeh Pegah Aledavoud,
- Mehdi Ghanbarlou,
- Bagher Larijani and
- Mohammad Mahdavi
Beilstein J. Org. Chem. 2023, 19, 1471–1502, doi:10.3762/bjoc.19.106
- low reactivity of these phthalimides, 10 mol % of catalyst was required. Cross-coupling reaction of sulfoximines 44 with N‑(arylthio)succinimides 1 catalyzed by a nanomaterial containing hexagonal boron nitride (h-BN) and γ-cyclodextrin-supported copper(II) acetate (h-BN@γ-CD@Cu(OAc)2) was developed
- functionalization of aryl C(sp2)–H bonds. FeCl3-catalyzed carbosulfenylation of unactivated alkenes. Copper-catalyzed electrophilic thiolation of organozinc halides. h-BN@Copper(II) nanomaterial catalyzed cross-coupling reaction of sulfoximines and N‑(arylthio)succinimide. AlCl3‑mediated cyclization and
Graphical Abstract
Scheme 1: Sulfur-containing bioactive molecules.
Scheme 2: Scandium-catalyzed synthesis of thiosulfonates.
Scheme 3: Palladium-catalyzed aryl(alkyl)thiolation of unactivated arenes.
Scheme 4: Catalytic cycle for Pd-catalyzed aryl(alkyl)thiolation of unactivated arenes.
Scheme 5: Iron- or boron-catalyzed C–H arylthiation of substituted phenols.
Scheme 6: Iron-catalyzed azidoalkylthiation of alkenes.
Scheme 7: Plausible mechanism for iron-catalyzed azidoalkylthiation of alkenes.
Scheme 8: BF3·Et2O‑mediated electrophilic cyclization of aryl alkynoates.
Scheme 9: Tentative mechanism for BF3·Et2O‑mediated electrophilic cyclization of aryl alkynoates.
Scheme 10: Construction of 6-substituted benzo[b]thiophenes.
Scheme 11: Plausible mechanism for construction of 6-substituted benzo[b]thiophenes.
Scheme 12: AlCl3‑catalyzed cyclization of N‑arylpropynamides with N‑sulfanylsuccinimides.
Scheme 13: Synthetic utility of AlCl3‑catalyzed cyclization of N‑arylpropynamides with N‑sulfanylsuccinimides.
Scheme 14: Sulfenoamination of alkenes with sulfonamides and N-sulfanylsuccinimides.
Scheme 15: Lewis acid/Brønsted acid controlled Pd-catalyzed functionalization of aryl C(sp2)–H bonds.
Scheme 16: Possible mechanism for Lewis acid/Brønsted acid controlled Pd-catalyzed functionalization of aryl C...
Scheme 17: FeCl3-catalyzed carbosulfenylation of unactivated alkenes.
Scheme 18: Copper-catalyzed electrophilic thiolation of organozinc halides.
Scheme 19: h-BN@Copper(II) nanomaterial catalyzed cross-coupling reaction of sulfoximines and N‑(arylthio)succ...
Scheme 20: AlCl3‑mediated cyclization and sulfenylation of 2‑alkyn-1-one O‑methyloximes.
Scheme 21: Lewis acid-promoted 2-substituted cyclopropane 1,1-dicarboxylates with sulfonamides and N-(arylthio...
Scheme 22: Lewis acid-mediated cyclization of β,γ-unsaturated oximes and hydrazones with N-(arylthio/seleno)su...
Scheme 23: Credible pathway for Lewis acid-mediated cyclization of β,γ-unsaturated oximes with N-(arylthio)suc...
Scheme 24: Synthesis of 4-chalcogenyl pyrazoles via chalcogenation/cyclization of α,β-alkynic hydrazones.
Scheme 25: Controllable synthesis of 3-thiolated pyrroles and pyrrolines.
Scheme 26: Possible mechanism for controllable synthesis of 3-thiolated pyrroles and pyrrolines.
Scheme 27: Co-catalyzed C2-sulfenylation and C2,C3-disulfenylation of indole derivatives.
Scheme 28: Plausible catalytic cycle for Co-catalyzed C2-sulfenylation and C2,C3-disulfenylation of indoles.
Scheme 29: C–H thioarylation of electron-rich arenes by iron(III) triflimide catalysis.
Scheme 30: Difunctionalization of alkynyl bromides with thiosulfonates and N-arylthio succinimides.·
Scheme 31: Suggested mechanism for difunctionalization of alkynyl bromides with thiosulfonates and N-arylthio ...
Scheme 32: Synthesis of thioesters, acyl disulfides, ketones, and amides by N-thiohydroxy succinimide esters.
Scheme 33: Proposed mechanism for metal-catalyzed selective acylation and acylthiolation.
Scheme 34: AlCl3-catalyzed synthesis of 3,4-bisthiolated pyrroles.
Scheme 35: α-Sulfenylation of aldehydes and ketones.
Scheme 36: Acid-catalyzed sulfetherification of unsaturated alcohols.
Scheme 37: Enantioselective sulfenylation of β-keto phosphonates.
Scheme 38: Organocatalyzed sulfenylation of 3‑substituted oxindoles.
Scheme 39: Sulfenylation and chlorination of β-ketoesters.
Scheme 40: Intramolecular sulfenoamination of olefins.
Scheme 41: Plausible mechanism for intramolecular sulfenoamination of olefins.
Scheme 42: α-Sulfenylation of 5H-oxazol-4-ones.
Scheme 43: Metal-free C–H sulfenylation of electron-rich arenes.
Scheme 44: TFA-promoted C–H sulfenylation indoles.
Scheme 45: Proposed mechanism for TFA-promoted C–H sulfenylation indoles.
Scheme 46: Organocatalyzed sulfenylation and selenenylation of 3-pyrrolyloxindoles.
Scheme 47: Organocatalyzed sulfenylation of S-based nucleophiles.
Scheme 48: Conjugate Lewis base Brønsted acid-catalyzed sulfenylation of N-heterocycles.
Scheme 49: Mechanism for activation of N-sulfanylsuccinimide by conjugate Lewis base Brønsted acid catalyst.
Scheme 50: Sulfenylation of deconjugated butyrolactams.
Scheme 51: Intramolecular sulfenofunctionalization of alkenes with phenols.
Scheme 52: Organocatalytic 1,3-difunctionalizations of Morita–Baylis–Hillman carbonates.
Scheme 53: Organocatalytic sulfenylation of β‑naphthols.
Scheme 54: Acid-promoted oxychalcogenation of o‑vinylanilides with N‑(arylthio/arylseleno)succinimides.
Scheme 55: Lewis base/Brønsted acid dual-catalytic C–H sulfenylation of aryls.
Scheme 56: Lewis base-catalyzed sulfenoamidation of alkenes.
Scheme 57: Cyclization of allylic amide using a Brønsted acid and tetrabutylammonium chloride.
Scheme 58: Catalytic electrophilic thiocarbocyclization of allenes with N-thiosuccinimides.
Scheme 59: Suggested mechanism for electrophilic thiocarbocyclization of allenes with N-thiosuccinimides.
Scheme 60: Chiral chalcogenide-catalyzed enantioselective hydrothiolation of alkenes.
Scheme 61: Proposed mechanism for chalcogenide-catalyzed enantioselective hydrothiolation of alkenes.
Scheme 62: Organocatalytic sulfenylation for synthesis a diheteroatom-bearing tetrasubstituted carbon centre.
Scheme 63: Thiolative cyclization of yne-ynamides.
Scheme 64: Synthesis of alkynyl and acyl disulfides from reaction of thiols with N-alkynylthio phthalimides.
Scheme 65: Oxysulfenylation of alkenes with 1-(arylthio)pyrrolidine-2,5-diones and alcohols.
Scheme 66: Arylthiolation of arylamines with (arylthio)-pyrrolidine-2,5-diones.
Scheme 67: Catalyst-free isothiocyanatoalkylthiation of styrenes.
Scheme 68: Sulfenylation of (E)-β-chlorovinyl ketones toward 3,4-dimercaptofurans.
Scheme 69: HCl-promoted intermolecular 1, 2-thiofunctionalization of aromatic alkenes.
Scheme 70: Possible mechanism for HCl-promoted 1,2-thiofunctionalization of aromatic alkenes.
Scheme 71: Coupling reaction of diazo compounds with N-sulfenylsuccinimides.
Scheme 72: Multicomponent reactions of disulfides with isocyanides and other nucleophiles.
Scheme 73: α-Sulfenylation and β-sulfenylation of α,β-unsaturated carbonyl compounds.
Application of N-heterocyclic carbene–Cu(I) complexes as catalysts in organic synthesis: a review
- Nosheen Beig,
- Varsha Goyal and
- Raj K. Bansal
Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102
- respectively, incorporating NHC–Cu(I) bromide and Cu(II) phenoxymine coordination. These complexes could be independently prepared through transmetallation by reacting NHC–AgBr 74 with copper(II) precursors Cu(SO3CF3)2 or CuCl2·2H2O (Scheme 26) [32]. Oro and co-workers synthesized new NHC–CuX complexes 78a,b
Graphical Abstract
Scheme 1: In situ generation of imidazolylidene carbene.
Scheme 2: Hg(II) complex of NHC.
Scheme 3: Isolable and bottlable carbene reported by Arduengo [3].
Scheme 4: First air-stable carbene synthesized by Arduengo in 1992 [5].
Figure 1: General structure of an NHC.
Figure 2: Stabilization of an NHC by donation of the lone pair electrons into the vacant p-orbital (LUMO) at ...
Figure 3: Abnormal NHC reported by Bertrand [8,9].
Figure 4: Cu(d) orbital to σ*C-N(NHC) interactions in NHC–CuX complexes computed at the B3LYP/def2-SVP level ...
Figure 5: Molecular orbital contributions to the NHC–metal bond.
Scheme 5: Synthesis of NHC–Cu(I) complexes by deprotonation of NHC precursors with a base.
Scheme 6: Synthesis of [NHC–CuX] complexes.
Scheme 7: Synthesis of [(ICy)CuX] and [(It-Bu)CuX] complexes.
Scheme 8: Synthesis of iodido-bridged copper–NHC complexes by deprotonation of benzimidazolium salts reported...
Scheme 9: Synthesis of copper complexes by deprotonation of triazolium salts.
Scheme 10: Synthesis of thiazolylidene–Cu(I) complex by deprotonation with KOt-Bu.
Scheme 11: Preparation of NHC–Cu(I) complexes.
Scheme 12: Synthesis of methylmalonic acid-derived anionic [(26a,b)CuCl]Li(THF)2 and zwitterionic (28) heterol...
Scheme 13: Synthesis of diaminocarbene and diamidocarbene (DAC)–Cu(I) complexes.
Scheme 14: Synthesis of the cationic (NHC)2Cu(I) complex 39 from benzimidazolium salts 38 with tetrakis(aceton...
Scheme 15: Synthesis of NHC and ADC (acyclic diamino carbenes) Cu(I) hexamethyldisilazide complexes reported b...
Scheme 16: Synthesis of NHC–copper(I) complexes using an acetylacetonate-functionalized imidazolium zwitterion...
Scheme 17: Synthesis of NHC–Cu(I) complexes through deprotonation of azolium salts with Cu2O.
Scheme 18: Synthesis of NHC–CuBr complex through deprotonation with Cu2O reported by Kolychev [31].
Scheme 19: Synthesis of chiral NHC–CuBr complexes from phenoxyimine-imidazolium salts reported by Douthwaite a...
Scheme 20: Preparation of linear neutral NHC–CuCl complexes through the use of Cu2O. For abbreviations, please...
Scheme 21: Synthesis of abnormal-NHC–copper(I) complexes by Bertrand, Cazin and co-workers [35].
Scheme 22: Microwave-assisted synthesis of thiazolylidene/benzothiazolylidene–CuBr complexes by Bansal and co-...
Scheme 23: Synthesis of NHC–CuX complexes through transmetallation.
Scheme 24: Preparation of six- or seven-membered NHC–Cu(I) complexes through transmetalation from Ag(I) comple...
Scheme 25: Synthesis of 1,2,3-triazolylidene–CuCl complexes through transmetallation of Ag(I) complexes genera...
Scheme 26: Synthesis of NHC–copper complexes having both Cu(I) and Cu(II) units through transmetalation report...
Scheme 27: Synthesis of new [(IPr(CH2)3Si(OiPr)3)CuX] complexes and anchoring on MCM-41.
Scheme 28: Synthesis of bis(trimethylsilyl)phosphide–Cu(I)–NHC complexes through ligand displacement.
Scheme 29: Synthesis of silyl- and stannyl [(NHC)Cu−ER3] complexes.
Scheme 30: Synthesis of amido-, phenolato-, thiophenolato–Cu(NHC) complexes.
Scheme 31: Synthesis of first isolable NHC–Cu–difluoromethyl complexes reported by Sanford et al. [44].
Scheme 32: Synthesis of NHC–Cu(I)–bifluoride complexes reported by Riant, Leyssens and co-workers [45].
Scheme 33: Conjugate addition of Et2Zn to enones catalyzed by an NHC–Cu(I) complex reported by Woodward in 200...
Scheme 34: Hydrosilylation of a carbonyl group.
Scheme 35: NHC–Cu(I)-catalyzed hydrosilylation of ketones reported by Nolan et al. [48,49].
Scheme 36: Application of chiral NHC–CuCl complex 104 for the enantioselective hydrosilylation of ketones.
Scheme 37: Hydrosilylation reactions catalyzed by NHC–Cu(Ot-Bu) complexes.
Scheme 38: NHC–CuCl catalyzed carbonylative silylation of alkyl halides.
Scheme 39: Nucleophilic conjugate addition to an activated C=C bond.
Figure 6: Molecular electrostatic potential maps (MESP) of two NHC–CuX complexes computed at the B3LYP/def2-S...
Scheme 40: Conjugate addition of Grignard reagents to 3-alkyl-substituted cyclohexenones catalyzed by a chiral...
Scheme 41: NHC–copper complex-catalyzed conjugate addition of Grignard reagent to 3-substituted hexenone repor...
Scheme 42: Conjugate addition or organoaluminum reagents to β-substituted cyclic enones.
Scheme 43: Conjugate addition of boronates to acyclic α,β-unsaturated carboxylic esters, ketones, and thioeste...
Scheme 44: NHC–Cu(I)-catalyzed hydroboration of an allene reported by Hoveyda [63].
Scheme 45: Conjugate addition of Et2Zn to cyclohexenone catalyzed by NHC–Cu(I) complex derived from benzimidaz...
Scheme 46: Asymmetric conjugate addition of diethylzinc to 3-nonen-2-one catalyzed by NHC–Cu complexes derived...
Scheme 47: General scheme of a [3 + 2] cycloaddition reaction.
Scheme 48: [3 + 2] Cycloaddition of azides with alkynes catalyzed by NHC–Cu(I) complexes reported by Diez-Gonz...
Scheme 49: Application of NHC–CuCl/N-donor combination to catalyze the [3 + 2] cycloaddition of benzyl azide w...
Scheme 50: [3 + 2] Cycloaddition of azides with acetylenes catalyzed by bis(NHC)–Cu complex 131 and mixed NHC–...
Figure 7: NHC–CuCl complex 133 as catalyst for the [3 + 2] cycloaddition of alkynes with azides at room tempe...
Scheme 51: [3 + 2] Cycloaddition of a bulky azide with an alkynylpyridine using [(NHC)Cu(μ-I)2Cu(NHC)] copper ...
Scheme 52: [3 + 2] Cycloaddition of benzyl azide with phenylacetylene under homogeneous and heterogeneous cata...
Scheme 53: [3 + 2] Cycloaddition of benzyl azide with acetylenes catalyzed by bisthiazolylidene dicopper(I) co...
Figure 8: Copper (I)–NHC linear coordination polymer 137 and its conversion into tetranuclear (138) and dinuc...
Scheme 54: An A3 reaction.
Scheme 55: Synthesis of SiO2-immobilized NHC–Cu(I) catalyst 141 and its application in the A3-coupling reactio...
Scheme 56: Preparation of dual-purpose Ru@SiO2–[(NHC)CuCl] catalyst system 142 developed by Bordet, Leitner an...
Scheme 57: Application of the catalyst system Ru@SiO2–[Cu(NHC)] 142 to the one-pot tandem A3 reaction and hydr...
Scheme 58: A3 reaction of phenylacetylene with secondary amines and aldehydes catalyzed by benzothiazolylidene...
Figure 9: Kohn–Sham HOMOs of phenylacetylene and NHC–Cu(I)–phenylacetylene complex computed at the B3LYP/def2...
Figure 10: Energies of the FMOs of phenylacetylene, iminium ion, and NHC–Cu(I)–phenylacetylene complex compute...
Scheme 59: NHC–Cu(I) catalyzed diboration of ketones 147 by reacting with bis(pinacolato)diboron (148) reporte...
Scheme 60: Protoboration of terminal allenes catalyzed by NHC–Cu(I) complexes reported by Hoveyda and co-worke...
Scheme 61: NHC–CuCl-catalyzed borylation of α-alkoxyallenes to give 2-boryl-1,3-butadienes.
Scheme 62: Regioselective hydroborylation of propargylic alcohols and ethers catalyzed by NHC–CuCl complexes 1...
Scheme 63: NHC–CuOt-Bu-catalyzed semihydrogenation and hydroborylation of alkynes.
Scheme 64: Enantioselective NHC–Cu(I)-catalyzed hydroborations of 1,1-disubstituted aryl olefins reported by H...
Scheme 65: Enantioselective NHC–Cu(I)-catalyzed hydroboration of exocyclic 1,1-disubstituted alkenes reported ...
Scheme 66: Markovnikov-selective NHC–CuOH-catalyzed hydroboration of alkenes and alkynes reported by Jones et ...
Scheme 67: Dehydrogenative borylation and silylation of styrenes catalyzed by NHC–CuOt-Bu complexes developed ...
Scheme 68: N–H/C(sp2)–H carboxylation catalyzed by NHC–CuOH complexes.
Scheme 69: C–H Carboxylation of benzoxazole and benzothiazole derivatives with CO2 using a 1,2,3-triazol-5-yli...
Scheme 70: Use of Cu(I) complex derived from diethylene glycol-functionalized imidazo[1,5,a] pyridin-3-ylidene...
Scheme 71: Allylation and alkenylation of polyfluoroarenes and heteroarenes catalyzed by NHC–Cu(I) complexes r...
Scheme 72: Enantioselective C(sp2)–H allylation of (benz)oxazoles and benzothiazoles with γ,γ-disubstituted pr...
Scheme 73: C(sp2)–H arylation of arenes catalyzed by dual NHC–Cu/NHC–Pd catalytic system.
Scheme 74: C(sp2)–H Amidation of (hetero)arenes with N-chlorocarbamates/N-chloro-N-sodiocarbamates catalyzed b...
Scheme 75: NHC–CuI catalyzed thiolation of benzothiazoles and benzoxazoles.
One-pot nucleophilic substitution–double click reactions of biazides leading to functionalized bis(1,2,3-triazole) derivatives
- Hans-Ulrich Reissig and
- Fei Yu
Beilstein J. Org. Chem. 2023, 19, 1399–1407, doi:10.3762/bjoc.19.101
- benzyl azide 3 in situ from benzyl bromide (5) and sodium azide and to directly trap the intermediate with alkyne 2. Under conditions summarized in reaction 3 of Scheme 2 we obtained the desired 1,2,3-triazole derivative 3 in 82% yield. Copper(II) sulfate pentahydrate (0.07 equivalents based on 2) in the
- allowed to lower the reaction temperature from 60 °C to 40 °C, but it also induced full consumption of the intermediate biazide derived from dihalide 11 (Scheme 4, reaction 3); 0.2 equiv of copper(II) sulfate pentahydrate, 0.4 equiv of sodium ascorbate and 0.4 equiv of ʟ-proline in very little of
Graphical Abstract
Scheme 1: Earlier approaches to multivalent carbohydrate mimetics B, D or F based on enantiopure aminopyran a...
Scheme 2: Synthesis of model compound 3 under conventional conditions and as a one-pot process employing benz...
Scheme 3: One-pot reaction employing enantiopure alkynyl-substituted 1,2-oxazin-4-one derivative 6 leading to...
Scheme 4: One-pot reactions of dihalides 8 and 11 with sodium azide and alkyne 2 leading to symmetric divalen...
Scheme 5: One-pot reactions employing enantiopure alkynyl-substituted 1,2-oxazin-4-one derivative 6 leading t...
Scheme 6: One-pot reaction employing enantiopure alkynyl-substituted 1,2-oxazin-4-ol derivative 19 leading to...
Scheme 7: Reductive ring-openings of 1,2-oxazine derivatives 19 and 23 as simple model compounds by hydrogeno...
Scheme 8: Attempted reductive ring-openings of compound 21 by hydrogenolysis or by samarium diiodide leading ...
Radical ligand transfer: a general strategy for radical functionalization
- David T. Nemoto Jr,
- Kang-Jie Bian,
- Shih-Chieh Kao and
- Julian G. West
Beilstein J. Org. Chem. 2023, 19, 1225–1233, doi:10.3762/bjoc.19.90
- elimination-like pathway to afford unsaturated C–C bonds in the presence of copper(II) sulfate, presumably via competitive RPC to the carbocation followed by E1 olefination. Kochi also demonstrated that RLT can be combined with other radical generation strategies to enable new, non-biomimetic reactions to be
- enzymes consists of HAT on a C–H bond, followed by RLT with a hydroxy ligand. II: Kochi reported the oxidation of alkyl radicals through LMCT of copper(II) chloride and subsequent radical chlorine ligand transfer [26]. 1-Cyclohexene was also reported to be oxidized to the vicinal dichlorinated product
Graphical Abstract
Scheme 1: Overview of the RLT mechanism in nature and in literature. I: The radical rebound mechanism in cyto...
Scheme 2: Areas of recent work on RLT development and application in catalysis. I: Reported RLT pathways ofte...
Scheme 3: The incorporation of RLT catalysis in ATRA photocatalysis. I: The reported method is compatible wit...
Scheme 4: Pioneering and recent work on decarboxylative functionalization involving a posited RLT pathway. I:...
Scheme 5: Our lab reported decarboxylative azidation of aliphatic and benzylic acids. I: The reaction proceed...
Unravelling a trichloroacetic acid-catalyzed cascade access to benzo[f]chromeno[2,3-h]quinoxalinoporphyrins
- Chandra Sekhar Tekuri,
- Pargat Singh and
- Mahendra Nath
Beilstein J. Org. Chem. 2023, 19, 1216–1224, doi:10.3762/bjoc.19.89
- Chandra Sekhar Tekuri Pargat Singh Mahendra Nath Department of Chemistry, Faculty of Science, University of Delhi, Delhi 110 007, India 10.3762/bjoc.19.89 Abstract A facile one-pot four-component synthetic methodology is evolved to construct novel copper(II) benzo[f]chromeno[2,3-h
- ]quinoxalinoporphyrins in good yields via a sequential reaction of copper(II) 2,3-diamino-5,10,15,20-tetraarylporphyrins, 2-hydroxynaphthalene-1,4-dione, aromatic aldehydes, and dimedone in the presence of a catalytic amount of trichloroacetic acid in chloroform at 65 °C. Further, the newly prepared copper(II
- present study discloses an easy and first synthetic approach to build highly π-conjugated copper(II) benzo[f]chromeno[2,3-h]quinoxalinoporphyrins through a trichloroacetic acid-catalyzed one-pot four-component reaction of 2,3-diamino-5,10,15,20-tetraarylporphyrins, 2-hydroxynaphthalene-1,4-dione, aromatic
Graphical Abstract
Scheme 1: Synthesis of benzo[f]chromeno[2,3-h]quinoxalinoporphyrins 3–16.
Figure 1: Plausible mechanism for the formation of copper(II) benzo[f]chromeno[2,3-h]quinoxalinoporphyrins.
Scheme 2: Sequential synthesis of copper(II) benzo[f]chromeno[2,3-h]quinoxalinoporphyrin 3.
Figure 2: Electronic absorption spectra of copper(II) benzo[f]chromeno[2,3-h]quinoxalinoporphyrins 3–8 in CHCl...
Figure 3: Electronic absorption spectra of free-base benzo[f]chromeno[2,3-h]quinoxalinoporphyrins 9–13 in CHCl...
Figure 4: Electronic absorption spectra of zinc(II) benzo[f]chromeno[2,3-h]quinoxalinoporphyrins 14–16 in CHCl...
Figure 5: (a) Emission spectra of free-base benzo[f]chromeno[2,3-h]quinoxalinoporphyrins 9–13 and (b) emissio...
Photoredox catalysis harvesting multiple photon or electrochemical energies
- Mattia Lepori,
- Simon Schmid and
- Joshua P. Barham
Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81
Graphical Abstract
Figure 1: Oxidative and reductive activations of organic compounds harvesting photoredox catalysis.
Figure 2: General catalytic cycles of radical ion conPET (left) and radical ion e-PRC (right).
Figure 3: “Beginner’s guide”: comparison between advantages, capacities, and prospectives of conPET and PEC.
Figure 4: A) conPET reductive dehalogenation of aryl halides with PDI. B) Reductive C–H arylation with pyrrol...
Figure 5: A) Chromoselective mono- and disubstitution or polybrominated pyrimidines with pyrroles. B) Sequent...
Figure 6: A) Synthesis of pyrrolo[1,2-a]quinolines. B) Synthesis of ullazines.
Figure 7: A) Reductive phosphorylation of aryl halides via conPET. B) Selected examples from the substrate sc...
Figure 8: A) Reductive dehalogenation of aryl halides via conPET and selected examples from the substrate sco...
Figure 9: A) Reductive C–H arylation of aryl halides via conPET (top) and selected examples from the substrat...
Figure 10: A) Reductive hydrodehalogenation of aryl halides with Mes-Acr-BF4. B) Selected examples from the su...
Figure 11: A) Reductive hydrodechlorination of aryl chlorides with 4-DPAIPN. B) Proposed formation of CO2•−. C...
Figure 12: A) Reductive conPET borylation with 3CzEPAIPN (top) and selected examples from the substrate scope ...
Figure 13: Scale-up of conPET phosphorylation with 3CzEPAIPN.
Figure 14: A) Borylation of 1d. B) Characteristics and structure of PC1 with green and red parts showing the l...
Figure 15: A) Reductive C–H arylation scope with polysulfide conPET (top) and selected examples from the subst...
Figure 16: Scale-up of A) C–H arylation and B) dehaloborylation with polysulfide photocatalysis in continuous-...
Figure 17: A) Formation of [Ir1]0 and [Ir2]0 upon PET between [Ir1]+ and Et3N. B) Mechanism of multi-photon ta...
Figure 18: A) Reductive hydrodehalogenation of aryl halides via multi-photon tandem photocatalysis. B) Selecte...
Figure 19: A) Carbonylative amidation of aryl halides in continuous flow. B) Selected examples from the substr...
Figure 20: A) General scheme for reductive (RQ) and oxidative quenching (OQ) protocols using [FeIII(btz)3](PF6)...
Figure 21: A) Carbonylative amidation of alkyl iodides with [IrIII(ppy)2(dtbbpy)]PF6. B) Selected examples fro...
Figure 22: A) Carboxylative C–N bond cleavage in cyclic amines. B) Selected examples from the substrate scope....
Figure 23: A) Formal reduction of alkenes to alkanes via transfer hydrogenation. B) Selected examples from the...
Figure 24: A) Birch-type reduction of benzenes with PMP-BPI. B) Selected examples from the substrate scope (sc...
Figure 25: Proposed mechanism of the OH− mediated conPET Birch-type reduction of benzene via generation of sol...
Figure 26: Reductive detosylation of N-tosylated amides with Mes-Acr-BF4. B) Selected examples from the substr...
Figure 27: A) Reductive detosylation of N-tosyl amides by dual PRC. B) Selected examples from the substrate sc...
Figure 28: A) Mechanism of the dual PRC based on PET between [Cu(dap)2]+ and DCA. B) Mechanism of the dual PRC...
Figure 29: A) N–O bond cleavage in Weinreb amides with anthracene. B) N–O bond cleavage in Weinreb amides rely...
Figure 30: A) Pentafluorosulfanylation and fluoride elimination. B) Mechanism of the pentafluorosulfanylation ...
Figure 31: A) α-Alkoxypentafluorosulfanylation (top) and selected examples from the substrate scope (bottom). ...
Figure 32: A) Oxidative amination of arenes with azoles catalyzed by N-Ph PTZ. B) Selected examples from the s...
Figure 33: A) C(sp3)–H bond activation by HAT via chloride oxidation by *N-Ph PTZ•+. B) Proposed mechanism for...
Figure 34: A) Recycling e-PRC C–H azolation of electron-rich arenes with pyrazoles using Mes-Acr+ as a photoca...
Figure 35: A) Radical ion e-PRC direct oxidation of unactivated arenes using TAC+ as an electro-activated phot...
Figure 36: A) Radical ion e-PRC direct oxidation of unactivated arenes using TPA as an electro-activated photo...
Figure 37: Proposed mechanism (top) and mode of preassembly (bottom).
Figure 38: A) Possible preassemblies of reactive (left) vs unreactive (right) arenes. B) Calculated spin densi...
Figure 39: A) Recycling e-PRC C(sp2 )–H acetoxylation of arenes using DDQ as a photocatalyst. B) Proposed cata...
Figure 40: Gram scale hydroxylation of benzene in a recirculated flow setup.
Figure 41: A) Radical ion e-PRC vicinal diamination of alkylarenes using TAC+ as an electro-activated photocat...
Figure 42: A) Sequential oxygenation of multiple adjacent C–H bonds under radical ion e-PRC using TAC+ as an e...
Figure 43: A) Enantioselective recycling e-PRC cyanation of benzylic C–H bonds using ADQS as photocatalyst. B)...
Figure 44: Proposed tandem mechanism by Xu and co-workers.
Figure 45: A) Enantioselective recycling e-PRC decarboxylative cyanation using Cu(acac)2, Ce(OTf)3 and a box l...
Figure 46: A) Enantioselective recycling e-PRC benzylic cyanation using Cu(MeCN)4BF4, box ligand and anthraqui...
Figure 47: A) Radical ion e-PRC acetoxyhydroxylation of aryl olefins using TAC+ as an electro-activated photoc...
Figure 48: Selected examples from the substrate scope.
Figure 49: Photoelectrochemical acetoxyhydroxylation in a recirculated flow setup.
Figure 50: A) Radical ion e-PRC aminooxygenation of aryl olefins using TAC+ as an electro-activated photocatal...
Figure 51: A) Recycling e-PRC C–H alkylation of heteroarenes with organic trifluoroborates using Mes-Acr+ as p...
Figure 52: A) Recycling e-PRC decarboxylative C–H alkylation of heteroarenes using CeCl3·7H2O as catalyst. B) ...
Figure 53: A) Recycling e-PRC decarboxylative C–H alkylation of heteroarenes using Fe(NH4)2(SO4)2·6H2O as cata...
Figure 54: A) Recycling e-PRC C–H alkylation of heteroarenes with alkyl oxalates and 4CzIPN as photocatalyst. ...
Figure 55: A) Recycling e-PRC decarboxylative C–H carbamoylation of heteroarenes using 4CzIPN as photocatalyst...
Figure 56: A) Photoelectrochemical HAT-mediated hydrocarbon activation via the chlorine radical. B) Proposed m...
Figure 57: A) Selected examples from the substrate scope. B) Gram and decagram scale semi-continuous flow PEC ...
Figure 58: A) Photoelectrochemical HAT-mediated dehydrogenative coupling of benzothiazoles with aliphatic C–H ...
Figure 59: A) Photoelectrochemical HAT activation of ethers using electro-activated TAC+ as photocatalyst. B) ...
Figure 60: Selected examples from the substrate scope.
Figure 61: A) Photoelectrochemical HAT-mediated synthesis of alkylated benzimidazo-fused isoquinolinones using...
Figure 62: A) Decoupled photoelectrochemical cerium-catalyzed oxydichlorination of alkynes using CeCl3 as cata...
Figure 63: Proposed decoupled photoelectrochemical mechanism.
Figure 64: A) Decoupled photoelectrochemical ring-opening bromination of tertiary cycloalkanols using MgBr2 as...
Figure 65: A) Recycling e-PRC ring-opening functionalization of cycloalkanols using CeCl3 as catalyst. B) Prop...
Figure 66: Selected examples from the substrate scope of the PEC ring-opening functionalization.
Figure 67: A) Radical ion e-PRC reduction of chloro- and bromoarenes using DCA as catalyst and various accepto...
Figure 68: A) Screening of different phthalimide derivatives as catalyst for the e-PRC reduction of aryl halid...
Figure 69: Screening of different organic catalysts for the e-PRC reduction of trialkylanilium salts.
Figure 70: A) e-PRC reduction of phosphonated phenols and anilinium salts. B) Selected examples from the subst...
Figure 71: A) ConPET and e-PRC reduction of 4-bromobenzonitrile using a naphthalene diimide (NDI) precatalyst ...
Figure 72: A) Radical ion e-PRC reduction of phosphinated aliphatic alcohols with n-BuO-NpMI as catalyst. B) C...
Figure 73: Selected examples from the substrate scope.
Figure 74: A) Recycling e-PRC reductive dimerization of benzylic chlorides using a [Cu2] catalyst. B) Proposed...
Figure 75: A) Decoupled photoelectrochemical C–H alkylation of heteroarenes through deamination of Katritzky s...
Figure 76: Proposed mechanism by Chen and co-workers.
Strategies in the synthesis of dibenzo[b,f]heteropines
- David I. H. Maier,
- Barend C. B. Bezuidenhoudt and
- Charlene Marais
Beilstein J. Org. Chem. 2023, 19, 700–718, doi:10.3762/bjoc.19.51
- disorders) [16] (Figure 2). 10,11-Dihydrodibenzo[b,f]azepine-based ligand 7 and a methyl analogue thereof are known to form pincer complexes with Pd, Ir, Rh and Ln [5], whereas a copper(II) wagon wheel complex of 8 was reported in a molecular organic framework (MOF) (Figure 3) [6]. 4,4'-(5-(Pyridin-2-yl
Graphical Abstract
Figure 1: Dibenzo[b,f]azepine (1a), -oxepine (1b) and -thiepine (1c) as examples of dibenzo[b,f]heteropines (1...
Figure 2: Selected pharmaceuticals with the dibenzo[b,f]azepine skeleton.
Figure 3: Examples of 10,11-dihydrodibenzo[b,f]azepine-based ligands.
Figure 4: The dibenzo[b,f]azepine moiety in dyes with properties suitable for the use in organic light emitti...
Figure 5: Selective bioactive natural products (13–18) containing the dibenzo[b,f]oxepine scaffold and Novart...
Scheme 1: Retrosynthetic approach to 5H-dibenzo[b,f]azepine (1a) from nitrotoluene (22).
Scheme 2: Oxidative coupling of o-nitrotoluene (22) and reduction of 2,2'-dinitrobibenzyl (21) to form 2,2'-d...
Scheme 3: Synthesis of 10,11-dihydro-5H-dibenzo[b,f]azepine (2a) via amine condensation.
Scheme 4: Catalytic reduction of 10,11-dihydro-5H-dibenzo[b,f]azepine (2a).
Scheme 5: The Wagner–Meerwein rearrangement of acridin-9-ylmethanol (23) into 5H-dibenzo[b,f]azepine (1a).
Scheme 6: Oxidative ring expansion of 2-(9-xanthenyl)malonates 24.
Scheme 7: Ring expansion via C–H functionalisation.
Scheme 8: The synthesis of fluorinated 5H-dibenzo[b,f]azepine 38 from isatin (32).
Scheme 9: The synthesis of substituted dibenzo[b,f]azepines 43 from indoles 39.
Scheme 10: Retrosynthetic pathways to dibenzo[b,f]azepines via Buchwald–Hartwig amination.
Scheme 11: Synthesis of dibenzo[b,f]oxepine 54 and -azepine 55 derivatives via (i) Heck reaction and (ii) Buch...
Scheme 12: Double Buchwald–Hartwig amination and thioetherification in the synthesis of tricyclic azepines 60 ...
Scheme 13: Double Buchwald–Hartwig amination towards substituted dibenzoazepines 62.
Scheme 14: Double Buchwald–Hartwig amination towards 10,11-dihydro-5H-dibenzo[b,f]azepine derivatives 71.
Scheme 15: One-pot Suzuki coupling–Buchwald–Hartwig amination.
Scheme 16: One-pot Rh/Pd-catalysed synthesis of dihydropyridobenzazepines.
Scheme 17: A retrosynthetic pathway to dibenzo[b,f]azepines via Mizoroki–Heck reaction.
Scheme 18: One-pot domino Pd-catalyzed Mizoroki–Heck–Buchwald–Hartwig synthesis of dibenzo[b,f]azepines.
Scheme 19: Dibenzo[b,f]thiapine and -oxepine synthesis via SNAr (thio)etherification, Wittig methylenation and...
Scheme 20: A retrosynthetic pathway to dibenzo[b,f]oxepines via Ullmann coupling.
Scheme 21: Ullmann-type coupling in dibenzo[b,f]oxepine synthesis.
Scheme 22: Wittig reaction and Ullmann coupling as key steps in dihydrobenz[b,f]oxepine synthesis.
Scheme 23: Pd-catalysed dibenzo[b,f]azepine synthesis via norbornene azepine intermediate 109.
Scheme 24: A simple representation of olefin metathesis resulting in transalkylidenation.
Scheme 25: Ring-closing metathesis as key step in the synthesis of dibenzo[b,f]heteropines.
Scheme 26: Alkyne–aldehyde metathesis in the synthesis of dibenzo[b,f]heteropines.
Scheme 27: Hydroarylation of 9-(2-alkynylphenyl)-9H-carbazole derivatives.
Scheme 28: Oxidative coupling of bisphonium ylide intermediate to give pacharin (13).
Scheme 29: Preparation of 10,11-dihydrodibenzo[b,f]heteropines via intramolecular Wurtz reaction.
Scheme 30: Phenol deprotonation and intramolecular etherification in the synthesis of bauhinoxepine J.
Figure 6: Functionalisation of dibenzo[b,f]azepine.
Scheme 31: Palladium-catalysed N-arylation of dibenzo[b,f]azepine.
Scheme 32: Cu- and Ni-catalysed N-arylation.
Scheme 33: N-Alkylation of dibenzo[b,f]azepine (1a) and dihydrodibenzo[b,f]azepine (2a).
Scheme 34: Preparation of methoxyiminosilbene.
Scheme 35: Synthesis of oxcarbazepine (153) from methoxy iminostilbene 151.
Scheme 36: Ring functionalisation of dihydrodibenzo[b,f]azepine.
Enolates ambushed – asymmetric tandem conjugate addition and subsequent enolate trapping with conventional and less traditional electrophiles
- Péter Kisszékelyi and
- Radovan Šebesta
Beilstein J. Org. Chem. 2023, 19, 593–634, doi:10.3762/bjoc.19.44
- asymmetric conjugate addition. The magnesium enolates 56 then participated in a copper(II)-mediated intramolecular oxidative coupling to afford benzofused spirocyclic cycloalkanones 57 (Scheme 14) [45]. Our team became interested in domino reactions of metal enolates generated by Cu-catalyzed asymmetric
- basis for generating and trapping of reactive metal enolates. The conjugate addition of R3Al to cyclic enones catalyzed by a combination of copper(II) naphthenate (CuNaph) and SimplePhos ligand L19 led to the corresponding aluminum enolates. Alexakis and co-workers used these enolates in a Mannich-type
Graphical Abstract
Scheme 1: General scheme depicting tandem reactions based on an asymmetric conjugate addition followed by an ...
Scheme 2: Cu-catalyzed tandem conjugate addition of R2Zn/aldol reaction with chiral acetals.
Scheme 3: Cu-catalyzed asymmetric desymmetrization of cyclopentene-1,3-diones using a tandem conjugate additi...
Scheme 4: Stereocontrolled assembly of dialkylzincs, cyclic enones, and sulfinylimines utilizing a Cu-catalyz...
Scheme 5: Cu-catalyzed tandem conjugate addition/Mannich reaction (A). Access to chiral isoindolinones and tr...
Scheme 6: Cu-catalyzed tandem conjugate addition/nitro-Mannich reaction (A) with syn–anti or syn–syn selectiv...
Figure 1: Various chiral ligands utilized for the tandem conjugate addition/Michael reaction sequences.
Scheme 7: Cu-catalyzed tandem conjugate addition/Michael reaction: side-product formation with chalcone (A) a...
Scheme 8: Zn enolate trapping using allyl iodides (A), Stork–Jung vinylsilane reagents (B), and allyl bromide...
Scheme 9: Cu-catalyzed tandem conjugate addition/acylation through Li R2Zn enolate (A). A four-component coup...
Scheme 10: Selected examples for the Cu-catalyzed tandem conjugate addition/trifluoromethylthiolation sequence....
Scheme 11: Zn enolates trapped by vinyloxiranes: synthesis of allylic alcohols.
Scheme 12: Stereoselective cyclopropanation of Mg enolates formed by ACA of Grignard reagents to chlorocrotona...
Scheme 13: Domino aldol reactions of Mg enolates formed from coumarin and chromone.
Scheme 14: Oxidative coupling of ACA-produced Mg enolates.
Scheme 15: Tandem ACA of Grignard reagents to enones and Mannich reaction.
Scheme 16: Diastereodivergent Mannich reaction of Mg enolates with differently N-protected imines.
Scheme 17: Tandem Grignard–ACA–Mannich using Taddol-based phosphine-phosphite ligands.
Scheme 18: Tandem reaction of Mg enolates with aminomethylating reagents.
Scheme 19: Tandem reaction composed of Grignard ACA to alkynyl enones.
Scheme 20: Rh/Cu-catalyzed tandem reaction of diazo enoates leading to cyclobutanes.
Scheme 21: Tandem Grignard-ACA of cyclopentenones and alkylation of enolates.
Scheme 22: Tandem ACA of Grignard reagents followed by enolate trapping reaction with onium compounds.
Scheme 23: Mg enolates generated from unsaturated lactones in reaction with activated alkenes.
Scheme 24: Lewis acid mediated ACA to amides and SN2 cyclization of a Br-appended enolate.
Scheme 25: Trapping reactions of aza-enolates with Michael acceptors.
Scheme 26: Si enolates generated by TMSOTf-mediated ACA of Grignard reagents and enolate trapping reaction wit...
Scheme 27: Trapping reactions of enolates generated from alkenyl heterocycles (A) and carboxylic acids (B) wit...
Scheme 28: Reactions of heterocyclic Mg enolates with onium compounds.
Scheme 29: Synthetic transformations of cycloheptatrienyl and benzodithiolyl substituents.
Scheme 30: Aminomethylation of Al enolates generated by ACA of trialkylaluminum reagents.
Scheme 31: Trapping reactions of enolates with activated alkenes.
Scheme 32: Alkynylation of racemic aluminum or magnesium enolates.
Scheme 33: Trapping reactions of Zr enolates generated by Cu-ACA of organozirconium reagents.
Scheme 34: Chloromethylation of Zr enolates using the Vilsmeier–Haack reagent.
Scheme 35: Tandem conjugate borylation with subsequent protonation or enolate trapping by an electrophile.
Scheme 36: Tandem conjugate borylation/aldol reaction of cyclohexenones.
Scheme 37: Selected examples for the tandem asymmetric borylation/intramolecular aldol reaction; synthesis of ...
Scheme 38: Cu-catalyzed tandem methylborylation of α,β-unsaturated phosphine oxide in the presence of (R,Sp)-J...
Scheme 39: Cu-catalyzed tandem transannular conjugated borylation/aldol cyclization of macrocycles containing ...
Scheme 40: Stereoselective tandem conjugate borylation/Mannich cyclization: selected examples (A) and a multi-...
Scheme 41: Some examples of Cu-catalyzed asymmetric tandem borylation/aldol cyclization (A). Application to di...
Scheme 42: Atropisomeric P,N-ligands used in tandem conjugate borylation/aldol cyclization sequence.
Scheme 43: Selected examples for the enantioselective Cu-catalyzed borylation/intramolecular Michael addition ...
Scheme 44: Selected examples for the preparation of enantioenriched spiroindanes using a Cu-catalyzed tandem c...
Scheme 45: Enantioselective conjugate borylation of cyclobutene-1-carboxylic acid diphenylmethyl ester 175 wit...
Scheme 46: Cu-catalyzed enantioselective tandem conjugate silylation of α,β-unsaturated ketones with subsequen...
Scheme 47: Cu-catalyzed enantioselective tandem conjugate silylation of α,β-unsaturated ketones with subsequen...
Scheme 48: Cu-catalyzed tandem conjugate silylation/aldol condensation. The diastereoselectivity is controlled...
Scheme 49: Chiral Ru-catalyzed three-component coupling reaction.
Scheme 50: Rh-Phebox complex-catalyzed reductive cyclization and subsequent reaction with Michael acceptors th...
Scheme 51: Rh-catalyzed tandem asymmetric conjugate alkynylation/aldol reaction (A) and subsequent spiro-cycli...
Scheme 52: Rh-bod complex-catalyzed tandem asymmetric conjugate arylation/intramolecular aldol addition (A). S...
Scheme 53: Co-catalyzed C–H-bond activation/asymmetric conjugate addition/aldol reaction.
Scheme 54: (Diisopinocampheyl)borane-promoted 1,4-hydroboration of α,β-unsaturated morpholine carboxamides and...
Figure 2: Some examples of total syntheses that have been recently reviewed.
Scheme 55: Stereoselective synthesis of antimalarial prodrug (+)-artemisinin utilizing a tandem conjugate addi...
Scheme 56: Amphilectane and serrulatane diterpenoids: preparation of chiral starting material via asymmetric t...
Scheme 57: Various asymmetric syntheses of pleuromutilin and related compounds based on a tandem conjugate add...
Scheme 58: Total synthesis of glaucocalyxin A utilizing a tandem conjugate addition/acylation reaction sequenc...
Scheme 59: Installation of the exocyclic double bond using a tandem conjugate addition/aminomethylation sequen...
Scheme 60: Synthesis of the taxol core using a tandem conjugate addition/enolate trapping sequence with Vilsme...
Scheme 61: Synthesis of the tricyclic core of 12-epi-JBIR-23/24 utilizing a Rh-catalyzed asymmetric conjugate ...
Scheme 62: Total synthesis of (−)-peyssonoside A utilizing a Cu-catalyzed enantioselective tandem conjugate ad...
CuAAC-inspired synthesis of 1,2,3-triazole-bridged porphyrin conjugates: an overview
- Dileep Kumar Singh
Beilstein J. Org. Chem. 2023, 19, 349–379, doi:10.3762/bjoc.19.29
- . First, copper and zinc derivatives of the porphyrin-coumarin conjugates 11a–20a were synthesized in excellent yields by the click reaction between copper(II)-2-azido-5,10,15,20-tetraphenylporphyrin (4) or zinc(II)-2-azidomethyl-5,10,15,20-tetraphenylporphyrin (5) and various alkyne-substituted coumarins
Graphical Abstract
Figure 1: Alkyne–azide "click reaction".
Figure 2: β- and meso-triazole-linked porphyrin.
Scheme 1: Synthesis of β-triazole-linked porphyrins 3a–c.
Scheme 2: Synthesis of β-triazole-bridged porphyrin-coumarin conjugates 11–20.
Scheme 3: Synthesis of β-triazole-bridged porphyrin-xanthone conjugates 23–27 and xanthone-bridged β-triazolo...
Scheme 4: Synthesis of meso-triazoloporphyrins 32a–c and triazole-bridged diporphyrins 34.
Scheme 5: Synthesis of meso-triazole-linked porphyrin-ferrocene conjugates 37a–d.
Scheme 6: Synthesis of meso-triazole-linked porphyrin conjugates 40a,b and 41a,b.
Scheme 7: Synthesis of meso-triazole-linked glycoporphyrins 43a–c.
Scheme 8: Synthesis of meso-triazole-linked porphyrin-coumarin conjugates 44–48.
Scheme 9: Synthesis of meso-triazole-bridged porphyrin-DNA conjugate 50.
Scheme 10: Synthesis of meso-linked porphyrin-triazole conjugates 53 and 57.
Scheme 11: Synthesis of meso-triazole-linked porphyrin-corrole conjugate 60.
Scheme 12: Synthesis of porphyrin conjugates 64a,b and 67a,b. Reaction conditions: (i) CuSO4, sodium ascorbate...
Scheme 13: Synthesis of meso-triazole-bridged porphyrin-quinolone conjugates 70a–e.
Scheme 14: Synthesis of meso-triazole-linked porphyrin-fluorescein dyad 73.
Scheme 15: Synthesis of meso-triazole-linked porphyrin-carborane conjugates 76a,b.
Scheme 16: Synthesis of meso-triazole-bridged porphyrin-BODIPY conjugates 78 and 80.
Scheme 17: Synthesis of meso-triazole-linked cationic porphyrin conjugates 85 and 87. Reaction conditions: (i)...
Scheme 18: Synthesis of meso-triazole-cobalt-porphyrin diimine-dioxime conjugate 91. Reactions conditions: (i)...
Scheme 19: Synthesis of triazole-linked porphyrin-bearing N-doped graphene hybrid 96.
Scheme 20: Synthesis of meso-triazole-linked porphyrin-fullerene dyads 100a–d and 104a,b.
Scheme 21: Synthesis of meso-triazole-bridged diporphyrin conjugates 107 and 108.
Scheme 22: Synthesis of porphyrin-ruthenium (II) conjugates 112a,b and 116a,b. Reaction conditions: (i) Zn(OAc)...
Scheme 23: Synthesis of meso-triazole-linked porphyrin dyad 119 and triad 121.
Scheme 24: Synthesis of di-triazole-bridged porphyrin-β-CD conjugate 126.
Scheme 25: Synthesis of meso-triazole-bridged porphyrin star trimer 129.
Scheme 26: Synthesis of 1,2,3-triazole-linked porphyrin-β-CD conjugates 131a,b.
Scheme 27: Synthesis of tritriazole-bridged porphyrin-lantern-DNA sequence 134.
Scheme 28: Synthesis of meso-triazole-linked porphyrin-polymer conjugates 137 and 139.
Scheme 29: Synthesis of triazole-linked capped porphyrin 142; Reaction conditions: method A: 10% H2O in THF, C...
Scheme 30: Synthesis of meso-tetratriazole-linked porphyrin-maleimine conjugates 145a–c.
Scheme 31: Synthesis of meso-tetratriazole-linked porphyrin-cholic acid complex 148a,b.
Scheme 32: Synthesis of meso-tetratriazole-linked porphyrin conjugates 151–153.
Scheme 33: Synthesis of meso-tetratrizole-porphyrin-carborane conjugates 155, 156 and 158a–c.
Scheme 34: Synthesis of meso-tetratriazole-porphyrin-cardanol conjugates 160 and 162.
Scheme 35: Synthesis of meso-tetratriazole-linked porphyrin-BODIPY conjugate 164.
Scheme 36: Synthesis of meso-tetratriazole-linked porphyrin-β-CD conjugates 166a,b.
Scheme 37: Synthesis of tetratriazole-bridged meso-arylporphyrins 171a–c and 172a–c.
Scheme 38: Synthesis of octatriazole-bridged porphyrin-β-CD conjugate 174 and porphyrin-adamantane conjugates ...
Combining the best of both worlds: radical-based divergent total synthesis
- Kyriaki Gennaiou,
- Antonios Kelesidis,
- Maria Kourgiantaki and
- Alexandros L. Zografos
Beilstein J. Org. Chem. 2023, 19, 1–26, doi:10.3762/bjoc.19.1
- polyene 14 (prepared in two steps) in multigram quantities [23]. The reaction employed a divided cell with substoichiometric amounts of magnesium(II) acetate (0.5 equiv) and catalytic copper(II) 3,5-diisopropylsalicylate (0.02 equiv) to allow the redox radical cyclization of polyene in 42% yield. A Tsuji
Graphical Abstract
Scheme 1: The power of radical retrosynthesis and the tactic of divergent total synthesis.
Figure 1: Evolution of radical chemistry for organic synthesis.
Scheme 2: Divergent total synthesis of α-pyrone-diterpenoids (Baran).
Scheme 3: Divergent synthesis of pyrone diterpenoids by merged chemoenzymatic and radical synthesis (part I, ...
Scheme 4: Divergent synthesis of pyrone diterpenoids by merged chemoenzymatic and radical synthesis (part II,...
Scheme 5: Divergent synthesis of drimane-type hydroquinone meroterpenoids (Li).
Scheme 6: Divergent synthesis of natural products isolated from Dysidea avara (Lu).
Scheme 7: Divergent synthesis of kaurene-type terpenoids (Lei).
Scheme 8: Divergent synthesis of 6-oxabicyclo[3.2.1]octane meroterpenoids (Lou).
Scheme 9: Divergent synthesis of crinipellins by radical-mediated Dowd–Backwith rearrangement (Xie and Ding).
Scheme 10: Divergent total synthesis of Galbulimima alkaloids (Shenvi).
Scheme 11: Divergent synthesis of eburnane alkaloids (Qin).
Scheme 12: Divergent synthesis of Aspidosperma alkaloids (Boger).
Scheme 13: Photoredox based synthesis of (−)-FR901483 (160) and (+)-TAN1251C (162, Gaunt).
Scheme 14: Divergent synthesis of bipolamines (Maimone).
Scheme 15: Flow chemistry divergency between aporphine and morphinandione alkaloids (Felpin).
Scheme 16: Divergent synthesis of pyrroloazocine natural products (Echavarren).
Scheme 17: Using TEMPO to stabilize radicals for the divergent synthesis of pyrroloindoline natural products (...
Scheme 18: Radical pathway for preparation of lignans (Zhu).
Scheme 19: Divergent synthesis of DBCOD lignans (Lumb).
