Search for "iridium" in Full Text gives 124 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2025, 21, 854–863, doi:10.3762/bjoc.21.69
Graphical Abstract
Figure 1: A) Energy transfer catalysis of alkenes in organic synthesis. B) Energy transfer catalysis of conju...
Figure 2: Probing boron effects on reactivity (A) and confirming the generation of a photostationary state eq...
Figure 3: Probing EnT catalysis enabled [2 + 2] cycloaddition of simple alkenylboronic esters.
Scheme 1: Establishing the substrate scope. Conditions: 3 (1 equiv), xanthone (20 mol %), MeCN (0.03 M), unde...
Scheme 2: A) Product derivatization and B) transition-metal EnT catalysis. Reaction conditions A): 4d (1 equi...
Beilstein J. Org. Chem. 2025, 21, 639–658, doi:10.3762/bjoc.21.51
Graphical Abstract
Scheme 1: Representative transition-metal catalysis for allylic substitution.
Scheme 2: Formation of stereogenic centers in copper-catalyzed allylic alkylation reactions.
Scheme 3: Copper-mediated, stereospecific SN2-selective allylic substitution through retentive transmetalatio...
Scheme 4: ZnCl2-promoted stereospecific SN2' allylic substitution of secondary alkylcopper species via sequen...
Scheme 5: Temperature and time-dependent configurational stability of chiral secondary organocopper species.
Scheme 6: DFT analysis of B–C bond lengths in various boronate complexes and correlation with reactivity.
Scheme 7: Copper-catalyzed stereospecific allylic alkylation of secondary alkylboronic esters via tert-butyll...
Scheme 8: Copper-catalyzed stereospecific allylic alkylation of chiral tertiary alkylboronic esters via adama...
Scheme 9: DFT-calculated energy surface for boron-to-copper transmetalation of either the tert-butyl group or...
Scheme 10: CuH-catalyzed enantioselective allylic substitution and postulated catalytic cycle.
Scheme 11: CuH-catalyzed enantioselective allylic substitution of vinylarenes.
Scheme 12: CuH-catalyzed stereoselective allylic substitution of vinylboronic esters.
Scheme 13: (a) Generation of chiral copper species via enantioselective CuH addition to vinylBpin. (b) Regardi...
Scheme 14: CuH-catalyzed enantioselective allylic substitution of 1‐trifluoromethylalkenes with 18-crown-6.
Scheme 15: CuH-catalyzed enantioselective allylic substitution of terminal alkynes.
Scheme 16: Copper-catalyzed enantiotopic-group-selective allylic substitution of 1,1-diborylalkanes.
Scheme 17: (a) Computational and (b) experimental studies to elucidate the mechanistic details of the enantiot...
Scheme 18: Copper-catalyzed regio-, diastereo- and enantioselective allylic substitution of 1,1-diborylalkanes....
Scheme 19: (a) Experimental and (b) computational studies to understand the stereoselectivities in oxidative a...
Beilstein J. Org. Chem. 2025, 21, 296–326, doi:10.3762/bjoc.21.22
Graphical Abstract
Figure 1: Influence of the metal center M (Fe, Ru, Os) on the position of the MLCT and MC (metal-centered) ab...
Scheme 1: Red-light-mediated ring-closing metathesis through activation of a ruthenium catalyst by an osmium ...
Scheme 2: Photocatalyzed polymerization of dicylopentadiene mediated with red or blue light.
Figure 2: Comparison between [Ru(bpy)3]2+ and [Os(tpy)2]2+ in a photocatalyzed trifluoromethylation reaction:...
Scheme 3: Red-light photocatalyzed C–N cross-coupling reaction by T. Rovis et al. (SET = single-electron tran...
Figure 3: Red-light-mediated aryl oxidative addition with a bismuthinidene complex.
Scheme 4: Red-light-mediated reduction of aryl derivatives by O. S. Wenger et al. (PC = photocatalyst, anh = ...
Scheme 5: Red-light-mediated aryl halides reduction with an isoelectronic chromium complex (TDAE = tetrakis(d...
Scheme 6: Red-light-photocatalyzed trifluoromethylation of styrene derivatives with Umemoto’s reagent and a p...
Scheme 7: Red-light-mediated energy transfer for the cross-dehydrogenative coupling of N-phenyltetrahydroisoq...
Scheme 8: Red-light-mediated oxidative cyanation of tertiary amines with a phthalocyanin zinc complex.
Scheme 9: Formation of dialins and tetralins via a red-light-photocatalyzed reductive decarboxylation mediate...
Scheme 10: Oxidation of β-citronellol (28) via energy transfer mediated by a red-light activable silicon phtha...
Scheme 11: Formation of alcohol derivatives 32 from boron compounds 31 using chlorophyll (chl) as a red-light-...
Scheme 12: Red-light-driven reductive dehalogenation of α-halo ketones mediated by a thiaporphyrin photocataly...
Figure 4: Photoinduced electron transfer-reversible addition-fragmentation chain transfer polymerization medi...
Figure 5: Recent examples of red-light-mediated photocatalytic reactions with traditional organic dyes.
Figure 6: Squaraine photocatalysts used by Goddard et al. and aza-Henry reaction with squaraine-based photoca...
Figure 7: Reactions described by Goddard et al. involving 40 as the photocatalyst.
Figure 8: Various structures of squaraine derivatives used to initiate photopolymerizations.
Figure 9: Naturally occurring cyanins.
Figure 10: Influence of the structure on the photophysical properties of a cyanin dye.
Figure 11: NIR-light-mediated aza-Henry reaction photocatalyzed by 46.
Scheme 13: Photocatalyzed arylboronic acids oxidation by 46.
Figure 12: Cyanin structures synthetized and characterized by Goddard et al. (redox potentials given against s...
Figure 13: N,N′-Di-n-propyl-1,13-dimethoxyquinacridinium (55) with its redox potentials at its ground state an...
Scheme 14: Dual catalyzed C(sp2)–H arylation of 57 using DMQA 55 as the red-light-absorbing photocatalyst.
Scheme 15: Red-light-mediated aerobic oxidation of arylboronic acids 59 into phenols 60 via the use of DMQA as...
Figure 14: Red-light-photocatalyzed reactions proposed by Gianetti et al. using DMQA as the photocatalyst.
Scheme 16: Simultaneous release of NO and production of superoxide (O2•−) and their combination yielding the p...
Figure 15: Palladium porphyrin complex as the photoredox catalyst and the NO releasing substrate are linked in...
Scheme 17: Uncaging of compound 69 which is a microtubule depolymerizing agent using near IR irradiation. The ...
Scheme 18: Photochemical uncaging of drugs protected with a phenylboronic acid derivative using near IR irradi...
Scheme 19: Photoredox catalytical generation of aminyl radicals with near IR irradiation for the transfer of b...
Scheme 20: Photoredox catalytical fluoroalkylation of tryptophan moieties.
Figure 16: Simultaneous absorption of two photons of infrared light of low energy enables electronic excitatio...
Scheme 21: Uncaging Ca2+ ions using two-photon excitation with near infrared light.
Beilstein J. Org. Chem. 2025, 21, 200–216, doi:10.3762/bjoc.21.12
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.
Beilstein J. Org. Chem. 2024, 20, 2784–2798, doi:10.3762/bjoc.20.234
Graphical Abstract
Figure 1: (A) Structures of tetrasubstituted 5,10,15,20-tetraphenylporphyrin (TPP, 1), dodecasubstituted 2,3,...
Scheme 1: Reaction scheme for the synthesis of OET-xBrPPs and subsequent Ni(II) metalation.
Figure 2: Substrates used for the investigations for the Suzuki–Miyaura coupling reactions.
Scheme 2: Scope of arm-extended dodecasubstituted porphyrins synthesized via modification of the meso-para-ph...
Scheme 3: Scope of arm-extended dodecasubstituted porphyrins synthesized via reaction at the meso-meta-phenyl...
Scheme 4: Attempts of arm-extension of dodecasubstituted porphyrins at the meso-ortho-phenyl position.
Scheme 5: Borylation and subsequent Suzuki–Miyaura coupling of porphyrin 13.
Figure 3: View of the molecular structure of compounds 26 (top left) and 27 (top right) with atomic displacem...
Figure 4: Left: packing diagram of 27 viewed normal to the c-axis showing the channels in the lattice with th...
Figure 5: Left: view of part 0 2 in the molecular structure of the α2β2-atropisomer, 11 in the crystal, hydro...
Figure 6: Schematic representation of porphyrin 37 showing a doubly intercalated structure.
Beilstein J. Org. Chem. 2024, 20, 1614–1622, doi:10.3762/bjoc.20.144
Graphical Abstract
Figure 1:
Correlating computed values and experimental pKa values for 695 compounds. r: Pearson correlation ...
Figure 2: ML-predicted pKa values vs QM-computed pKa values of the held-out test set (155 compounds; 789 pKa ...
Scheme 1: Predicting the reaction site for three different reactions from the out-of-sample dataset from Reax...
Figure 3: Predicting the site of borylation for a set of six experimentally reported borylation reactions [45]. A...
Beilstein J. Org. Chem. 2024, 20, 1527–1547, doi:10.3762/bjoc.20.137
Graphical Abstract
Figure 1: A) Benzylic fluorides in bioactive compounds, with B) the relative BDEs of different benzylic C–H b...
Figure 2: Base-mediated benzylic fluorination with Selectfluor.
Figure 3: Sonochemical base-mediated benzylic fluorination with Selectfluor.
Figure 4: Mono- and difluorination of nitrogen-containing heteroaromatic benzylic substrates.
Figure 5: Palladium-catalysed benzylic C–H fluorination with N-fluoro-2,4,6-trimethylpyridinium tetrafluorobo...
Figure 6: Palladium-catalysed, PIP-directed benzylic C(sp3)–H fluorination of α-amino acids and proposed mech...
Figure 7: Palladium-catalysed monodentate-directed benzylic C(sp3)–H fluorination of α-amino acids.
Figure 8: Palladium-catalysed bidentate-directed benzylic C(sp3)–H fluorination.
Figure 9: Palladium-catalysed benzylic fluorination using a transient directing group approach. Ratio refers ...
Figure 10: Outline for benzylic C(sp3)–H fluorination via radical intermediates.
Figure 11: Iron(II)-catalysed radical benzylic C(sp3)–H fluorination using Selectfluor.
Figure 12: Silver and amino acid-mediated benzylic fluorination.
Figure 13: Copper-catalysed radical benzylic C(sp3)–H fluorination using NFSI.
Figure 14: Copper-catalysed C(sp3)–H fluorination of benzylic substrates with electrochemical catalyst regener...
Figure 15: Iron-catalysed intramolecular fluorine-atom-transfer from N–F amides.
Figure 16: Vanadium-catalysed benzylic fluorination with Selectfluor.
Figure 17: NDHPI-catalysed radical benzylic C(sp3)–H fluorination with Selectfluor.
Figure 18: Potassium persulfate-mediated radical benzylic C(sp3)–H fluorination with Selectfluor.
Figure 19: Benzylic fluorination using triethylborane as a radical chain initiator.
Figure 20: Heterobenzylic C(sp3)–H radical fluorination with Selectfluor.
Figure 21: Benzylic fluorination of phenylacetic acids via a charge-transfer complex. NMR yields in parenthese...
Figure 22: Oxidative radical photochemical benzylic C(sp3)–H strategies.
Figure 23: 9-Fluorenone-catalysed photochemical radical benzylic fluorination with Selectfluor.
Figure 24: Xanthone-photocatalysed radical benzylic fluorination with Selectfluor II.
Figure 25: 1,2,4,5-Tetracyanobenzene-photocatalysed radical benzylic fluorination with Selectfluor.
Figure 26: Xanthone-catalysed benzylic fluorination in continuous flow.
Figure 27: Photochemical phenylalanine fluorination in peptides.
Figure 28: Decatungstate-photocatalyzed versus AIBN-initiated selective benzylic fluorination.
Figure 29: Benzylic fluorination using organic dye Acr+-Mes and Selectfluor.
Figure 30: Palladium-catalysed benzylic C(sp3)–H fluorination with nucleophilic fluoride.
Figure 31: Manganese-catalysed benzylic C(sp3)–H fluorination with AgF and Et3N·3HF and proposed mechanism. 19...
Figure 32: Iridium-catalysed photocatalytic benzylic C(sp3)–H fluorination with nucleophilic fluoride and N-ac...
Figure 33: Iridium-catalysed photocatalytic benzylic C(sp3)–H fluorination with TBPB HAT reagent.
Figure 34: Silver-catalysed, amide-promoted benzylic fluorination via a radical-polar crossover pathway.
Figure 35: General mechanism for oxidative electrochemical benzylic C(sp3)–H fluorination.
Figure 36: Electrochemical benzylic C(sp3)–H fluorination with HF·amine reagents.
Figure 37: Electrochemical benzylic C(sp3)–H fluorination with 1-ethyl-3-methylimidazolium trifluoromethanesul...
Figure 38: Electrochemical benzylic C(sp3)–H fluorination of phenylacetic acid esters with HF·amine reagents.
Figure 39: Electrochemical benzylic C(sp3)–H fluorination of triphenylmethane with PEG and CsF.
Figure 40: Electrochemical benzylic C(sp3)–H fluorination with caesium fluoride and fluorinated alcohol HFIP.
Figure 41: Electrochemical secondary and tertiary benzylic C(sp3)–H fluorination. GF = graphite felt. DCE = 1,...
Figure 42: Electrochemical primary benzylic C(sp3)–H fluorination of electron-poor toluene derivatives. Ring f...
Figure 43: Electrochemical primary benzylic C(sp3)–H fluorination utilizing pulsed current electrolysis.
Beilstein J. Org. Chem. 2024, 20, 1348–1375, doi:10.3762/bjoc.20.119
Graphical Abstract
Figure 1: Generation of alkyl and acyl radicals via C–O bond breaking.
Figure 2: General photocatalytic mechanism.
Scheme 1: Photoredox-catalyzed hydroacylation of olefins with aliphatic carboxylic acids.
Scheme 2: Acylation–aromatization of p-quinone methides using carboxylic acids.
Scheme 3: Visible-light-induced deoxygenation–defluorination for the synthesis of γ,γ-difluoroallylic ketones....
Scheme 4: Photochemical hydroacylation of azobenzenes with carboxylic acids.
Scheme 5: Photoredox-catalyzed synthesis of flavonoids.
Scheme 6: Synthesis of O-thiocarbamates and photocatalytic reduction of O-thiocarbamates.
Scheme 7: Deoxygenative borylation of alcohols.
Scheme 8: Trifluoromethylation of O-alkyl thiocarbonyl substrates.
Scheme 9: Redox-neutral radical coupling reactions of alkyl oxalates and Michael acceptors.
Scheme 10: Visible-light-catalyzed and Ni-mediated syn-alkylarylation of alkynes.
Scheme 11: 1,2-Alkylarylation of alkenes with aryl halides and alkyl oxalates.
Scheme 12: Deoxygenative borylation of oxalates.
Scheme 13: Coupling of N-phthalimidoyl oxalates with various acceptors.
Scheme 14: Cross-coupling of O-alkyl xanthates with aryl halides via dual photoredox and nickel catalysis.
Scheme 15: Deoxygenative borylation of secondary alcohol.
Scheme 16: Deoxygenative alkyl radical generation from alcohols under visible-light photoredox conditions.
Scheme 17: Deoxygenative alkylation via alkoxy radicals against hydrogenation or β-fragmentation.
Scheme 18: Direct C–O bond activation of benzyl alcohols.
Scheme 19: Deoxygenative arylation of alcohols using NHC to activate alcohols.
Scheme 20: Deoxygenative conjugate addition of alcohol using NHC as alcohol activator.
Scheme 21: Synthesis of polysubstituted aldehydes.
Beilstein J. Org. Chem. 2024, 20, 1111–1166, doi:10.3762/bjoc.20.98
Graphical Abstract
Scheme 1: General scheme of the borrowing hydrogen (BH) or hydrogen auto-transfer (HA) methodology.
Scheme 2: General scheme for C–N bond formation. A) Traditional cross-couplings with alkyl or aryl halides. B...
Figure 1: Manganese pre-catalysts used for the N-alkylation of amines with alcohols.
Scheme 3: Manganese(I)-pincer complex Mn1 used for the N-alkylation of amines with alcohols and methanol.
Scheme 4: N-Methylation of amines with methanol using Mn2.
Scheme 5: C–N-Bond formation with amines and methanol using PN3P-Mn complex Mn3 reported by Sortais et al. [36]. a...
Scheme 6: Base-assisted synthesis of amines and imines with Mn4. Reaction assisted by A) t-BuOK and B) t-BuON...
Scheme 7: Coupling of alcohols and hydrazine via the HB approach reported by Milstein et al. [38]. aReaction time...
Scheme 8: Proposed mechanism for the coupling of alcohols and hydrazine catalyzed by Mn5.
Scheme 9: Phosphine-free manganese catalyst for N-alkylation of amines with alcohols reported by Balaraman an...
Scheme 10: N-Alkylation of sulfonamides with alcohols.
Scheme 11: Mn–NHC catalyst Mn6 applied for the N-alkylation of amines with alcohols. a3 mol % of Mn6 were used....
Scheme 12: N-Alkylation of amines with primary and secondary alcohols. a80 °C, b100 °C.
Scheme 13: Manganese(III)-porphyrin catalyst for synthesis of tertiary amines.
Scheme 14: Proposed mechanism for the alcohol dehydrogenation with Mn(III)-porphyrin complex Mn7.
Scheme 15: N-Methylation of nitroarenes with methanol using catalyst Mn3.
Scheme 16: Mechanism of manganese-catalyzed methylation of nitroarenes using Mn3 as the catalyst.
Scheme 17: Bidentate manganese complex Mn8 applied for the N-alkylation of primary anilines with alcohols. aOn...
Scheme 18: N-Alkylation of amines with alcohols in the presence of manganese salts and triphenylphosphine as t...
Scheme 19: N-Alkylation of diazo compounds with alcohols using catalyst Mn9.
Scheme 20: Proposed mechanism for the amination of alcohols with diazo compounds catalyzed by catalyst Mn9.
Scheme 21: Mn1 complex-catalyzed synthesis of polyethyleneimine from ethylene glycol and ethylenediamine.
Scheme 22: Bis-triazolylidene-manganese complex Mn10 for the N-alkylation of amines with alcohols.
Figure 2: Manganese complexes applied for C-alkylation reactions of ketones with alcohols.
Scheme 23: General scheme for the C–C bond formation with alcohols and ketones.
Scheme 24: Mn1 complex-catalyzed α-alkylation of ketones with primary alcohols.
Scheme 25: Mechanism for the Mn1-catalyzed alkylation of ketones with alcohols.
Scheme 26: Phosphine-free in situ-generated manganese catalyst for the α-alkylation of ketones with primary al...
Scheme 27: Plausible mechanism for the Mn-catalyzed α-alkylation of ketones with alcohols.
Scheme 28: α-Alkylation of esters, ketones, and amides using alcohols catalyzed by Mn11.
Scheme 29: Mono- and dialkylation of methylene ketones with primary alcohols using the Mn(acac)2/1,10-phenanth...
Scheme 30: Methylation of ketones with methanol and deuterated methanol.
Scheme 31: Methylation of ketones and esters with methanol. a50 mol % of t-BuOK were used, bCD3OD was used ins...
Scheme 32: Alkylation of ketones and secondary alcohols with primary alcohols using Mn4.
Scheme 33: Bidentate manganese-NHC complex Mn6 applied for the synthesis of alkylated ketones using alcohols.
Scheme 34: Mn1-catalyzed synthesis of substituted cycloalkanes by coupling diols and secondary alcohols or ket...
Scheme 35: Proposed mechanism for the synthesis of cycloalkanes via BH method.
Scheme 36: Synthesis of various cycloalkanes from methyl ketones and diols catalyze by Mn13. aReaction time wa...
Scheme 37: N,N-Amine–manganese complex (Mn13)-catalyzed alkylation of ketones with alcohols.
Scheme 38: Naphthyridine‑N‑oxide manganese complex Mn14 applied for the alkylation of ketones with alcohols. a...
Scheme 39: Proposed mechanism of the naphthyridine‑N‑oxide manganese complex (Mn14)-catalyzed alkylation of ke...
Scheme 40: α-Methylation of ketones and indoles with methanol using Mn15.
Scheme 41: α-Alkylation of ketones with primary alcohols using Mn16. aNMR yield.
Figure 3: Manganese complexes used for coupling of secondary and primary alcohols.
Scheme 42: Alkylation of secondary alcohols with primary alcohols catalyzed by phosphine-free catalyst Mn17. a...
Scheme 43: PNN-Manganese complex Mn18 for the alkylation of secondary alcohols with primary alcohols.
Scheme 44: Mechanism for the Mn-pincer catalyzed C-alkylation of secondary alcohols with primary alcohols.
Scheme 45: Upgrading of ethanol with methanol for isobutanol production.
Scheme 46: Mn-Pincer catalyst Mn19 applied for the β-methylation of alcohols with methanol. a2.0 mol % of Mn19...
Scheme 47: Functionalized ketones from primary and secondary alcohols catalyzed by Mn20. aMn20 (5 mol %), NaOH...
Scheme 48: Synthesis of γ-disubstituted alcohols and β-disubstituted ketones through Mn9-catalyzed coupling of...
Scheme 49: Proposed mechanism for the Mn9-catalyzed synthesis of γ-disubstituted alcohols and β-disubstituted ...
Scheme 50: Dehydrogenative coupling of ethylene glycol and primary alcohols catalyzed by Mn4.
Scheme 51: Mn18-cataylzed C-alkylation of unactivated esters and amides with alcohols.
Scheme 52: Alkylation of amides and esters using Mn21.
Scheme 53: α-Alkylation of nitriles with primary alcohols using in situ-generated manganese catalyst.
Scheme 54: Proposed mechanism for the α-alkylation of nitriles with primary alcohols.
Scheme 55: Mn9-catalyzed α-alkylation of nitriles with primary alcohols. a1,4-Dioxane was used as solvent, 24 ...
Figure 4: Manganese complexes used for alkylation of heterocyclic compounds.
Scheme 56: Aminomethylation of aromatic compounds with secondary amines and methanol catalyzed by Mn22.
Scheme 57: Regioselective alkylation of indolines with alcohols catalyzed by Mn9. aMn9 (4 mol %), 48 h.
Scheme 58: Proposed mechanism for the C- and N-alkylation of indolines with alcohols.
Scheme 59: C-Alkylation of methyl N-heteroarenes with primary alcohols catalyzed by Mn1. aTime was 60 h.
Scheme 60: C-Alkylation of oxindoles with secondary alcohols.
Scheme 61: Plausible mechanism for the Mn23-catalyzed C-alkylation of oxindoles with secondary alcohols.
Scheme 62: Synthesis of C-3-alkylated products by coupling alcohols with indoles and aminoalcohols.
Scheme 63: C3-Alkylation of indoles using Mn1.
Scheme 64: C-Methylation of indoles with Mn15 and methanol.
Scheme 65: α-Alkylation of 2-oxindoles with primary and secondary alcohols catalyzed by Mn25. aReaction carrie...
Scheme 66: Dehydrogenative alkylation of indolines with Mn1. aMn1 (5.0 mol %) was used.
Scheme 67: Synthesis of bis(indolyl)methane derivatives from indoles and alcohols catalyzed by Mn26. aMn26 (5....
Scheme 68: One-pot synthesis of pyrimidines via BH.
Scheme 69: Synthesis of pyrroles from alcohols and aminoalcohols using Mn4.
Scheme 70: Synthesis of pyrroles via multicomponent reaction catalyzed by Mn12.
Scheme 71: Friedländer quinoline synthesis using an in situ-generated phosphine-free manganese catalyst.
Scheme 72: Quinoline synthesis using bis-N-heterocyclic carbene-manganese catalyst Mn6.
Scheme 73: Quinoline synthesis using manganese(III)-porphyrin catalyst Mn7.
Scheme 74: Manganese-catalyzed tetrahydroquinoline synthesis via borrowing BH.
Scheme 75: Proposed mechanism for the manganese-catalyzed tetrahydroquinoline synthesis.
Scheme 76: Synthesis of C3-alkylated indoles using Mn24.
Scheme 77: Synthesis of C-3-alkylated indoles using Mn1.
Scheme 78: C–C Bond formation by coupling of alcohols and ylides.
Scheme 79: C-Alkylation of fluorene with alcohols catalyzed by Mn24.
Scheme 80: Proposed mechanism for the C-alkylation of fluorene with alcohols catalyzed by Mn24.
Scheme 81: α-Alkylation of sulfones using Mn-PNN catalyst Mn28.
Beilstein J. Org. Chem. 2024, 20, 701–713, doi:10.3762/bjoc.20.64
Graphical Abstract
Scheme 1: Overview of homopropargylic azides importance and strategies for azido-alkynylation.
Scheme 2: Screening of nucleophilic alkynes and investigation of the photocatalyst solubility. n.o = not obse...
Scheme 3: Selected scope entries of the azido-alkynylation. The data were already published in ref. [45].
Scheme 4: Unsuccessful examples. The conditions used are the same as in Scheme 3. The yields reported were determined...
Scheme 5: Proposed mechanism.
Beilstein J. Org. Chem. 2024, 20, 346–378, doi:10.3762/bjoc.20.35
Graphical Abstract
Scheme 1: Comparison between Barton and NHPI ester radical precursors.
Scheme 2: Overview of the mechanisms and activation modes involved in radical generation from RAEs.
Scheme 3: Common mechanisms in photocatalysis.
Scheme 4: A) Giese-type radical addition of NHPI esters mediated by a reductive quenching photocatalytic cycl...
Scheme 5: A) Minisci-type radical addition of NHPI esters. B) Reaction mechanism involving an “off-cycle” red...
Scheme 6: Activation of NHPI esters through hydrogen-bonding in an oxidative quenching photocatalytic cycle.
Scheme 7: SET activation of RAE facilitated by a Lewis acid catalyst.
Scheme 8: PCET activation of NHPI esters in the context of a radical-redox annulation.
Scheme 9: Activation enabled by a strong excited-state reductant catalyst and its application in the dearomat...
Scheme 10: Proposed formation of an intramolecular charge-transfer complex in the synthesis of (spiro)anellate...
Scheme 11: Formation of a charge-transfer complex between enamides and NHPI esters enabled by a chiral phospha...
Scheme 12: Activation of NHPI ester through the formation of photoactive EDA-complexes.
Scheme 13: A) EDA complex-mediated radical hydroalkylation reactions of NHPI esters. B) Proposed mechanism for...
Scheme 14: Proposed radical chain mechanism initiated by EDA-complex formation.
Scheme 15: A) Photoinduced decarboxylative borylation. B) Proposed radical chain mechanism.
Scheme 16: A) Activation of NHPI esters mediated by PPh3/NaI. B) Proposed catalytic cycle involving EDA-comple...
Scheme 17: A) Radical generation facilitated by EDA complex formation between PTH1 catalyst and NHPI esters. B...
Scheme 18: Proposed catalytic cycle for the difunctionalization of styrenes.
Scheme 19: Formation of a charge-transfer complex between NHPI esters and Cs2CO3 enables decarboxylative amina...
Scheme 20: 3-Acetoxyquinuclidine as catalytic donor in the activation of TCNHPI esters.
Scheme 21: A) Photoinduced Cu-catalyzed decarboxylative amination. B) Proposed catalytic cycle. C) Radical clo...
Scheme 22: A) Photoinduced Pd-catalyzed aminoalkylation of 1,4-dienes. B) Proposed catalytic cycle.
Scheme 23: A) TM-catalyzed decarboxylative coupling of NHPI esters and organometallic reagents. B) Representat...
Scheme 24: Synthetic applications of the TM-catalyzed decarboxylative coupling of NHPI esters and organometall...
Scheme 25: A) Ni-catalyzed cross-electrophile coupling of NHPI esters. B) Representative catalytic cycle.
Scheme 26: A) Synthetic applications of decarboxylative cross-electrophile couplings. B) Decarboxylative aryla...
Scheme 27: A) Activation of tetrachlorophthalimide redox-active esters enabled by a low-valency Bi complex. B)...
Scheme 28: Activation of NHPI esters mediated by Zn0 applied in a Z-selective alkenylation reaction.
Scheme 29: A) Activation of NHPI esters enabled by a pyridine-boryl radical species applied to the decarboxyla...
Scheme 30: A) Decarboxylative coupling of RAE and aldehydes enabled by NHC-catalyzed radical relay. B) Propose...
Scheme 31: A) Decarboxylative C(sp3)–heteroatom coupling reaction of NHPI esters under NHC catalysis B) The NH...
Scheme 32: A) Electrochemical Giese-type radical addition of NHPI esters. B) Reaction mechanism.
Scheme 33: Electrochemical Minisci-type radical addition of NHPI-esters.
Scheme 34: Ni-electrocatalytic cross-electrophile coupling of NHPI esters with aryl iodides.
Scheme 35: A) Decarboxylative arylation of NHPI esters under Ag-Ni electrocatalysis B) Formation of AgNP on th...
Scheme 36: Synthetic applications of decarboxylative couplings of NHPI esters under Ni-electrocatalysis.
Scheme 37: Examples of natural product syntheses in which RAEs were used in key C–C bond forming reactions.
Beilstein J. Org. Chem. 2023, 19, 1947–1956, doi:10.3762/bjoc.19.145
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)...
Beilstein J. Org. Chem. 2023, 19, 1289–1298, doi:10.3762/bjoc.19.95
Graphical Abstract
Figure 1: The molecular structures of the title compound 4BGIPN and the benchmark TADF emitter 4CzIPN.
Figure 2: Crystal structure for compound 4BGIPN in monoclinic form ((a) top view and (b) side view) where bla...
Figure 3: Full range cyclic voltammogram for 4BGIPN. Recorded using a glassy carbon electrode in THF solution...
Figure 4: UV–vis absorption spectra for compound 4BGIPN in various solvents.
Figure 5: Photoluminescence spectra for 4BGIPN at 295 and 77 K in (top left) MCH solution; (bottom left) Zeon...
Figure 6: Energy state diagram and natural transition orbitals HONTO and LUNTO for compound 4BGIPN in excited...
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.
Beilstein J. Org. Chem. 2023, 19, 918–927, doi:10.3762/bjoc.19.70
Graphical Abstract
Figure 1: (a) Transformations of DMAT to different classes of ergot alkaloids. (b) and (c) Strategies for the...
Scheme 1: Synthesis of compound 5.
Scheme 2: Photoredox-catalyzed radical decarboxylative cyclization of 5.
Figure 2: Proposed reaction mechanism for photoredox-catalyzed radical decarboxylative cyclization.
Scheme 3: Synthesis of tryptophan derivatives 8 and 10.
Figure 3: Proposed reaction mechanism for photoredox-catalyzed radical decarboxylative cyclization.
Scheme 4: Methylation of 11 and the formal total synthesis of (±)-6,7-secoagroclavine.
Beilstein J. Org. Chem. 2023, 19, 820–863, doi:10.3762/bjoc.19.62
Graphical Abstract
Figure 1: Representative examples of bioactive natural products and FDA-approved drugs containing a pyridine ...
Scheme 1: Classical and traditional methods for the synthesis of functionalized pyridines.
Scheme 2: Rare earth metal (Ln)-catalyzed pyridine C–H alkylation.
Scheme 3: Pd-catalyzed C–H alkylation of pyridine N-oxide.
Scheme 4: CuI-catalyzed C–H alkylation of N-iminopyridinium ylides with tosylhydrazones (A) and a plausible r...
Scheme 5: Zirconium complex-catalyzed pyridine C–H alkylation.
Scheme 6: Rare earth metal-catalyzed pyridine C–H alkylation with nonpolar unsaturated substrates.
Scheme 7: Heterobimetallic Rh–Al complex-catalyzed ortho-C–H monoalkylation of pyridines.
Scheme 8: Mono(phosphinoamido)-rare earth complex-catalyzed pyridine C–H alkylation.
Scheme 9: Rhodium-catalyzed pyridine C–H alkylation with acrylates and acrylamides.
Scheme 10: Ni–Al bimetallic system-catalyzed pyridine C–H alkylation.
Scheme 11: Iridium-catalyzed pyridine C–H alkylation.
Scheme 12: para-C(sp2)–H Alkylation of pyridines with alkenes.
Scheme 13: Enantioselective pyridine C–H alkylation.
Scheme 14: Pd-catalyzed C2-olefination of pyridines.
Scheme 15: Ru-catalyzed C-6 (C-2)-propenylation of 2-arylated pyridines.
Scheme 16: C–H addition of allenes to pyridines catalyzed by half-sandwich Sc metal complex.
Scheme 17: Pd-catalyzed stereodivergent synthesis of alkenylated pyridines.
Scheme 18: Pd-catalyzed ligand-promoted selective C3-olefination of pyridines.
Scheme 19: Mono-N-protected amino acids in Pd-catalyzed C3-alkenylation of pyridines.
Scheme 20: Amide-directed and rhodium-catalyzed C3-alkenylation of pyridines.
Scheme 21: Bimetallic Ni–Al-catalyzed para-selective alkenylation of pyridine.
Scheme 22: Arylboronic ester-assisted pyridine direct C–H arylation.
Scheme 23: Pd-catalyzed C–H arylation/benzylation with toluene.
Scheme 24: Pd-catalyzed pyridine C–H arylation with potassium aryl- and heteroaryltrifluoroborates.
Scheme 25: Transient activator strategy in pyridine C–H biarylation.
Scheme 26: Ligand-promoted C3-arylation of pyridine.
Scheme 27: Pd-catalyzed arylation of nicotinic and isonicotinic acids.
Scheme 28: Iron-catalyzed and imine-directed C–H arylation of pyridines.
Scheme 29: Pd–(bipy-6-OH) cooperative system-mediated direct pyridine C3-arylation.
Scheme 30: Pd-catalyzed pyridine N-oxide C–H arylation with heteroarylcarboxylic acids.
Scheme 31: Pd-catalyzed C–H cross-coupling of pyridine N-oxides with five-membered heterocycles.
Scheme 32: Cu-catalyzed dehydrative biaryl coupling of azine(pyridine) N-oxides and oxazoles.
Scheme 33: Rh(III)-catalyzed cross dehydrogenative C3-heteroarylation of pyridines.
Scheme 34: Pd-catalyzed C3-selective arylation of pyridines.
Scheme 35: Rhodium-catalyzed oxidative C–H annulation of pyridines to quinolines.
Scheme 36: Rhodium-catalyzed and NHC-directed C–H annulation of pyridine.
Scheme 37: Ni/NHC-catalyzed regio- and enantioselective C–H cyclization of pyridines.
Scheme 38: Rare earth metal-catalyzed intramolecular C–H cyclization of pyridine to azaindolines.
Scheme 39: Rh-catalyzed alkenylation of bipyridine with terminal silylacetylenes.
Scheme 40: Rollover cyclometallation in Rh-catalyzed pyridine C–H functionalization.
Scheme 41: Rollover pathway in Rh-catalyzed C–H functionalization of N,N,N-tridentate chelating compounds.
Scheme 42: Pd-catalyzed rollover pathway in bipyridine-6-carboxamides C–H arylation.
Scheme 43: Rh-catalyzed C3-acylmethylation of bipyridine-6-carboxamides with sulfoxonium ylides.
Scheme 44: Rh-catalyzed C–H functionalization of bipyridines with alkynes.
Scheme 45: Rh-catalyzed C–H acylmethylation and annulation of bipyridine with sulfoxonium ylides.
Scheme 46: Iridium-catalyzed C4-borylation of pyridines.
Scheme 47: C3-Borylation of pyridines.
Scheme 48: Pd-catalyzed regioselective synthesis of silylated dihydropyridines.
Beilstein J. Org. Chem. 2023, 19, 487–540, doi:10.3762/bjoc.19.38
Graphical Abstract
Figure 1: Ring-strain energies of homobicyclic and heterobicyclic alkenes in kcal mol−1. a) [2.2.1]-Bicyclic ...
Figure 2: a) Exo and endo face descriptions of bicyclic alkenes. b) Reactivity comparisons for different β-at...
Scheme 1: Ni-catalyzed ring-opening/cyclization cascade of heterobicyclic alkenes 1 with alkyl propiolates 2 ...
Scheme 2: Ni-catalyzed ring-opening/cyclization cascade of heterobicyclic alkenes 8 with β-iodo-(Z)-propenoat...
Scheme 3: Ni-catalyzed two- and three-component difunctionalizations of norbornene derivatives 15 with alkyne...
Scheme 4: Ni-catalyzed intermolecular three-component difunctionalization of oxabicyclic alkenes 1 with alkyn...
Scheme 5: Ni-catalyzed intermolecular three-component carboacylation of norbornene derivatives 15.
Scheme 6: Photoredox/Ni dual-catalyzed coupling of 4-alkyl-1,4-dihydropyridines 31 with heterobicyclic alkene...
Scheme 7: Photoredox/Ni dual-catalyzed coupling of α-amino radicals with heterobicyclic alkenes 30.
Scheme 8: Cu-catalyzed rearrangement/allylic alkylation of 2,3-diazabicyclo[2.2.1]heptenes 47 with Grignard r...
Scheme 9: Cu-catalyzed aminoboration of bicyclic alkenes 1 with bis(pinacolato)diboron (B2pin2) (53) and O-be...
Scheme 10: Cu-catalyzed borylalkynylation of oxabenzonorbornadiene (30b) with B2pin2 (53) and bromoalkynes 62.
Scheme 11: Cu-catalyzed borylacylation of bicyclic alkenes 1.
Scheme 12: Cu-catalyzed diastereoselective 1,2-difunctionalization of oxabenzonorbornadienes 30 for the synthe...
Scheme 13: Fe-catalyzed carbozincation of heterobicyclic alkenes 1 with arylzinc reagents 74.
Scheme 14: Co-catalyzed addition of arylzinc reagents of norbornene derivatives 15.
Scheme 15: Co-catalyzed ring-opening/dehydration of oxabicyclic alkenes 30 via C–H activation of arenes.
Scheme 16: Co-catalyzed [3 + 2] annulation/ring-opening/dehydration domino reaction of oxabicyclic alkenes 1 w...
Scheme 17: Co-catalyzed enantioselective carboamination of bicyclic alkenes 1 via C–H functionalization.
Scheme 18: Ru-catalyzed cyclization of oxabenzonorbornene derivatives with propargylic alcohols for the synthe...
Scheme 19: Ru-catalyzed coupling of oxabenzonorbornene derivatives 30 with propargylic alcohols and ethers 106...
Scheme 20: Ru-catalyzed ring-opening/dehydration of oxabicyclic alkenes via the C–H activation of anilides.
Scheme 21: Ru-catalyzed of azabenzonorbornadiene derivatives with arylamides.
Scheme 22: Rh-catalyzed cyclization of bicyclic alkenes with arylboronate esters 118.
Scheme 23: Rh-catalyzed cyclization of bicyclic alkenes with dienyl- and heteroaromatic boronate esters.
Scheme 24: Rh-catalyzed domino lactonization of doubly bridgehead-substituted oxabicyclic alkenes with seconda...
Scheme 25: Rh-catalyzed domino carboannulation of diazabicyclic alkenes with 2-cyanophenylboronic acid and 2-f...
Scheme 26: Rh-catalyzed synthesis of oxazolidinone scaffolds 147 through a domino ARO/cyclization of oxabicycl...
Scheme 27: Rh-catalyzed oxidative coupling of salicylaldehyde derivatives 151 with diazabicyclic alkenes 130a.
Scheme 28: Rh-catalyzed reaction of O-acetyl ketoximes with bicyclic alkenes for the synthesis of isoquinoline...
Scheme 29: Rh-catalyzed domino coupling reaction of 2-phenylpyridines 165 with oxa- and azabicyclic alkenes 30....
Scheme 30: Rh-catalyzed domino dehydrative naphthylation of oxabenzonorbornadienes 30 with N-sulfonyl 2-aminob...
Scheme 31: Rh-catalyzed domino dehydrative naphthylation of oxabenzonorbornadienes 30 with arylphosphine deriv...
Scheme 32: Rh-catalyzed domino ring-opening coupling reaction of azaspirotricyclic alkenes using arylboronic a...
Scheme 33: Tandem Rh(III)/Sc(III)-catalyzed domino reaction of oxabenzonorbornadienes 30 with alkynols 184 dir...
Scheme 34: Rh-catalyzed asymmetric domino cyclization and addition reaction of 1,6-enynes 194 and oxa/azabenzo...
Scheme 35: Rh/Zn-catalyzed domino ARO/cyclization of oxabenzonorbornadienes 30 with phosphorus ylides 201.
Scheme 36: Rh-catalyzed domino ring opening/lactonization of oxabenzonorbornadienes 30 with 2-nitrobenzenesulf...
Scheme 37: Rh-catalyzed domino C–C/C–N bond formation of azabenzonorbornadienes 30 with aryl-2H-indazoles 210.
Scheme 38: Rh/Pd-catalyzed domino synthesis of indole derivatives with 2-(phenylethynyl)anilines 212 and oxabe...
Scheme 39: Rh-catalyzed domino carborhodation of heterobicyclic alkenes 30 with B2pin2 (53).
Scheme 40: Rh-catalyzed three-component 1,2-carboamidation reaction of bicyclic alkenes 30 with aromatic and h...
Scheme 41: Pd-catalyzed diarylation and dialkenylation reactions of norbornene derivatives.
Scheme 42: Three-component Pd-catalyzed arylalkynylation reactions of bicyclic alkenes.
Scheme 43: Three-component Pd-catalyzed arylalkynylation reactions of norbornene and DFT mechanistic study.
Scheme 44: Pd-catalyzed three-component coupling N-tosylhydrazones 236, aryl halides 66, and norbornene (15a).
Scheme 45: Pd-catalyzed arylboration and allylboration of bicyclic alkenes.
Scheme 46: Pd-catalyzed, three-component annulation of aryl iodides 66, alkenyl bromides 241, and bicyclic alk...
Scheme 47: Pd-catalyzed double insertion/annulation reaction for synthesizing tetrasubstituted olefins.
Scheme 48: Pd-catalyzed aminocyclopropanation of bicyclic alkenes 1 with 5-iodopent-4-enylamine derivatives 249...
Scheme 49: Pd-catalyzed, three-component coupling of alkynyl bromides 62 and norbornene derivatives 15 with el...
Scheme 50: Pd-catalyzed intramolecular cyclization/ring-opening reaction of heterobicyclic alkenes 30 with 2-i...
Scheme 51: Pd-catalyzed dimer- and trimerization of oxabenzonorbornadiene derivatives 30 with anhydrides 268.
Scheme 52: Pd-catalyzed Catellani-type annulation and retro-Diels–Alder of norbornadiene 15b yielding fused xa...
Scheme 53: Pd-catalyzed hydroarylation and heteroannulation of urea-derived bicyclic alkenes 158 and aryl iodi...
Scheme 54: Access to fused 8-membered sulfoximine heterocycles 284/285 via Pd-catalyzed Catellani annulation c...
Scheme 55: Pd-catalyzed 2,2-bifunctionalization of bicyclic alkenes 1 generating spirobicyclic xanthone deriva...
Scheme 56: Pd-catalyzed Catellani-type annulation and retro-Diels–Alder of norbornadiene (15b) producing subst...
Scheme 57: Pd-catalyzed [2 + 2 + 1] annulation furnishing bicyclic-fused indanes 281 and 283.
Scheme 58: Pd-catalyzed ring-opening/ring-closing cascade of diazabicyclic alkenes 130a.
Scheme 59: Pd-NHC-catalyzed cyclopentannulation of diazabicyclic alkenes 130a.
Scheme 60: Pd-catalyzed annulation cascade generating diazabicyclic-fused indanones 292 and indanols 294.
Scheme 61: Pd-catalyzed skeletal rearrangement of spirotricyclic alkenes 176 towards large polycyclic benzofur...
Scheme 62: Pd-catalyzed oxidative annulation of aromatic enamides 298 and diazabicyclic alkenes 130a.
Scheme 63: Accessing 3,4,5-trisubstituted cyclopentenes 300, 301, 302 via the Pd-catalyzed domino reaction of ...
Scheme 64: Palladacycle-catalyzed ring-expansion/cyclization domino reactions of terminal alkynes and bicyclic...
Scheme 65: Pd-catalyzed carboesterification of norbornene (15a) with alkynes, furnishing α-methylene γ-lactone...
Beilstein J. Org. Chem. 2023, 19, 245–281, doi:10.3762/bjoc.19.23
Graphical Abstract
Figure 1: Examples of terpenes containing a bicyclo[3.6.0]undecane motif.
Figure 2: Commercially available first and second generation Grubbs and Hoveyda–Grubbs catalysts.
Figure 3: Examples of strategies to access the fusicoccan and ophiobolin tricyclic core structure by RCM.
Scheme 1: Synthesis of bicyclic core structure 12 of ophiobolin M (13) and cycloaraneosene (14).
Scheme 2: Synthesis of the core structure 21 of ophiobolins and fusicoccanes.
Scheme 3: Ring-closing metathesis attempts starting from thioester 22.
Scheme 4: Total synthesis of ent-fusicoauritone (28).
Figure 4: General structure of ophiobolins and congeners.
Scheme 5: Total synthesis of (+)-ophiobolin A (8).
Scheme 6: Investigation of RCM for the synthesis of ophiobolin A (8). Path A) RCM with TBDPS-protected alcoho...
Scheme 7: Synthesis of the core structure of cotylenin A aglycon, cotylenol (50).
Scheme 8: Synthesis of tricyclic core structure of fusicoccans.
Scheme 9: Total synthesis of (−)-teubrevin G (59).
Scheme 10: Synthesis of the core skeleton 63 of the basmane family.
Scheme 11: Total synthesis of (±)-schindilactone A (68).
Scheme 12: Total synthesis of dactylol (72).
Scheme 13: Ring-closing metathesis for the total synthesis of (±)-asteriscanolide (2).
Scheme 14: Synthesis of the simplified skeleton of pleuromutilin (1).
Scheme 15: Total synthesis of (−)-nitidasin (93) using a ring-closing metathesis to construct the eight-member...
Scheme 16: Total synthesis of (±)-naupliolide (97).
Scheme 17: Synthesis of the A-B ring structure of fusicoccane (101).
Scheme 18: First attempts of TRCM of dienyne substrates.
Scheme 19: TRCM on optimized substrates towards the synthesis of ophiobolin A (8).
Scheme 20: Tandem ring-closing metathesis for the synthesis of variecolin intermediates 114 and 115.
Scheme 21: Synthesis of poitediol (118) using the allylsilane ring-closing metathesis.
Scheme 22: Access to scaffold 122 by a NHK coupling reaction.
Scheme 23: Key step to construct the [5-8] bicyclooctanone core of aquatolide (4).
Scheme 24: Initial strategy to access aquatolide (4).
Scheme 25: Synthetic plan to cotylenin A (130).
Scheme 26: [5-8] Bicyclic structure of brachialactone (7) constructed by a Mizoroki–Heck reaction.
Scheme 27: Influence of the replacement of the allylic alcohol moiety.
Scheme 28: Formation of variecolin intermediate 140 through a SmI2-mediated Barbier-type reaction.
Scheme 29: SmI2-mediated ketyl addition. Pleuromutilin (1) eight-membered ring closure via C5–C14 bond formati...
Scheme 30: SmI2-mediated dialdehyde cyclization cascade of [5-8-6] pleuromutilin scaffold 149.
Scheme 31: A) Modular synthetic route to mutilin and pleuromutilin family members by Herzon’s group. B) Scaffo...
Scheme 32: Photocatalyzed oxidative ring expansion in pleuromutilin (1) total synthesis.
Scheme 33: Reductive radical cascade cyclization route towards (−)-6-epi-ophiobolin N (168).
Scheme 34: Reductive radical cascade cyclization route towards (+)-6-epi-ophiobolin A (173).
Scheme 35: Radical 8-endo-trig-cyclization of a xanthate precursor.
Figure 5: Structural representations of hypoestin A (177), albolic acid (178), and ceroplastol II (179) beari...
Scheme 36: Synthesis of the common [5-8-5] tricyclic intermediate of hypoestin A (177), albolic acid (178), an...
Scheme 37: Asymmetric synthesis of hypoestin A (177), albolic acid (178), and ceroplastol II (179).
Figure 6: Scope of the Pauson–Khand reaction.
Scheme 38: Nazarov cyclization revealing the fusicoauritone core structure 192.
Scheme 39: Synthesis of fusicoauritone (28) through Nazarov cyclization.
Scheme 40: (+)-Epoxydictymene (5) synthesis through a Nicholas cyclization followed by a Pauson–Khand reaction...
Scheme 41: Synthesis of aquatolide (4) by a Mukaiyama-type aldolisation.
Scheme 42: Tandem Wolff/Cope rearrangement furnishing the A-B bicyclic moiety 204 of variecolin.
Scheme 43: Asymmetric synthesis of the A-B bicyclic core 205 and 206 of variecolin.
Scheme 44: Formation of [5-8]-fused rings by cyclization under thermal activation.
Scheme 45: Construction of the [5-8-6] tricyclic core structure of variecolin (3) by Diels–Alder reaction.
Scheme 46: Synthesis of the [6-4-8-5]-tetracyclic skeleton by palladium-mediated cyclization.
Scheme 47: Access to the [5-8] bicyclic core structure of asteriscanolide (227) through rhodium-catalyzed cycl...
Scheme 48: Total syntheses of asterisca-3(15),6-diene (230) and asteriscanolide (2) with a Rh-catalyzed cycliz...
Scheme 49: Photocyclization of 2-pyridones to access the [5-8-5] backbone of fusicoccanes.
Scheme 50: Total synthesis of (+)-asteriscunolide D (245) and (+)-aquatolide (4) through photocyclization.
Scheme 51: Biocatalysis pathway to construct the [5-8-5] tricyclic scaffold of brassicicenes.
Scheme 52: Influence of the CotB2 mutant over the cyclization’s outcome of GGDP.
Beilstein J. Org. Chem. 2023, 19, 1–26, doi:10.3762/bjoc.19.1
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).
Beilstein J. Org. Chem. 2022, 18, 1707–1719, doi:10.3762/bjoc.18.181
Graphical Abstract
Figure 1: General structure of grayanane natural products.
Scheme 1: Grayanane biosynthesis.
Scheme 2: Matsumoto’s relay approach.
Scheme 3: Shirahama’s total synthesis of (–)-grayanotoxin III.
Scheme 4: Newhouse’s syntheses of fragments 25 and 29.
Scheme 5: Newhouse’s total synthesis of principinol D.
Scheme 6: Ding’s total synthesis of rhodomolleins XX and XXII.
Scheme 7: First key step of Luo’s strategy.
Scheme 8: Luo’s total synthesis of grayanotoxin III.
Scheme 9: Synthesis of principinol E and rhodomollein XX.
Scheme 10: William’s synthetic effort towards pierisformaside C.
Scheme 11: Hong’s synthetic effort towards rhodojaponin III.
Scheme 12: Recent strategies for grayanane synthesis.
Beilstein J. Org. Chem. 2022, 18, 1507–1517, doi:10.3762/bjoc.18.159
Graphical Abstract
Figure 1: Some new quinoline antibacterial drugs.
Figure 2: Cyclometalated iridium-catalyzed ADC reaction of o-aminobenzyl alcohols and secondary alcohols.
Figure 3: Gram-scale transformations.
Figure 4: Mechanistic investigation.
Figure 5: A speculated possible mechanism.
Beilstein J. Org. Chem. 2022, 18, 1311–1321, doi:10.3762/bjoc.18.136
Graphical Abstract
Figure 1: Chemical structures of (a) reported ionic TADF emitters for LEECs, (b) the MR-TADF emitter DiKTa an...
Scheme 1: Synthesis of DiKTa-OBuIm and DiKTa-DPA-OBuIm.
Figure 2: (a) HOMO and LUMO electron density distribution and orbital energies of DiKTa-OMe and DiKTa-DPA-OMe...
Figure 3: (a) Cyclic and differential pulse voltammograms measured in degassed MeCN with 0.1 M [n-Bu4N]PF6 as...
Figure 4: (a) Steady-state emission spectra of DiKTa-OBuIm and DiKTa-DPA-OBuIm in 1 wt % doped mCP films, λex...
Figure 5: (a) Electroluminescence spectra of DiKTa-OBuIm (green curve), DiKTa-DPA-OBuIm (red curve) and 1% of ...
Beilstein J. Org. Chem. 2022, 18, 1256–1263, doi:10.3762/bjoc.18.131
Graphical Abstract
Scheme 1: C3–Si bond functionalization of biomass-derived 3-silylated furfural platforms.
Scheme 2: Preparation of 3-silylated 2-furyl carbinols.
Scheme 3: C–Si bond functionalization of 2,3-disubstituted furyl carbinols by 1,4-silyl migration.
Scheme 4: Attempts of C3–Si bond functionalization promoted by intramolecular activation via alkoxide.
Scheme 5: Alkoxide-promoted cyclic siloxane formation from 2-[(3-benzyldimethylsilyl)furyl] carbinol 4c.
Scheme 6: TBAF-promoted cyclic siloxane formation from 2-[(3-benzyldimethylsilyl)furyl] carbinol 4c.
Scheme 7: Pd-catalyzed arylation of 2-[(3-benzyldimethylsilyl)furyl] carbinol 4c.
Scheme 8: Cu-catalyzed allylation and methylation of 2-[(3-benzyldimethylsilyl)furyl] carbinols. aCuI⋅PPh3 (1...
Beilstein J. Org. Chem. 2022, 18, 1055–1061, doi:10.3762/bjoc.18.107
Graphical Abstract
Scheme 1: Designed electrochemical hydrogenation of enones 1 with a PEM reactor.
Figure 1: Electrochemical setup of the PEM reactor: a) Electrochemical reduction system with the PEM reactor....
Figure 2: Reaction profile of the electrochemical hydrogenation of 1a with a PEM reactor using a) Pd/C and b)...
Scheme 2: Electrochemical hydrogenation of several enones 1 with a circulating PEM reactor using a Pd/C catho...
Scheme 3: Electrochemical hydrogenation of several enones 1 with a circulating PEM reactor using an Ir/C cath...
Scheme 4: Mechanistic studies.
Scheme 5: Electroreduction of 1a with the circulating PEM reactor using H2O as a proton source.
Beilstein J. Org. Chem. 2022, 18, 1040–1046, doi:10.3762/bjoc.18.105
Graphical Abstract
Scheme 1: Generation of N-acyliminium ion: previous and present works.
Scheme 2: Electrochemical amidomethylation of indoles 4 in DMA.
Scheme 3: Electrochemical amidomethylation of 3-methyl-1H-indole (7) in DMA.
Scheme 4: Electrochemical amidomethylation of N-methyl-1H-indole (4a) in DMF.
Scheme 5: Probable reaction pathway of the electrochemical amidomethylation.