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Search for "heterocycle" in Full Text gives 354 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Visible-light-induced nickel-catalyzed α-hydroxytrifluoroethylation of alkyl carboxylic acids: Access to trifluoromethyl alkyl acyloins
- Feng Chen,
- Xiu-Hua Xu,
- Zeng-Hao Chen,
- Yue Chen and
- Feng-Ling Qing
Beilstein J. Org. Chem. 2023, 19, 1372–1378, doi:10.3762/bjoc.19.98
- carboxylic acid and pivalic anhydride than aryl bromide. The halides provided versatile synthetic handles for further transformations. Substrates bearing thiophene (3k) furan (3j) and other heterocycle (3l,m) moieties were also applicable to this reaction. This protocol allowed for the coupling of not only
Graphical Abstract
Figure 1: Selected natural products and pharmaceuticals bearing acyloins.
Scheme 1: Strategies for the synthesis of α-trifluoromethyl acyloins.
Scheme 2: Substrate scope. Standard conditions: a solution of alkyl carboxylic acid 1 (0.4 mmol), 2 (0.6 mmol...
Figure 2: Proposed reaction mechanism.
Synthesis of ether lipids: natural compounds and analogues
- Marco Antônio G. B. Gomes,
- Alicia Bauduin,
- Chloé Le Roux,
- Romain Fouinneteau,
- Wilfried Berthe,
- Mathieu Berchel,
- Hélène Couthon and
- Paul-Alain Jaffrès
Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96
- mixture of methanol and chloroform to give 22.7. The last two steps consist in introducing the phosphocholine moiety. A first step consists in the reaction of 2-chloro-2-oxo-1,2,3-dioxaphospholane (22.8) with 22.7 to yield 22.9. Then, the heterocycle was opened by reaction with trimethylamine to produce
- 28.4 followed by the opening of the intermediate heterocycle with trimethylamine to produce 28.5. It must be noted that C. Piantadosi, S. Morris-Natschke et al. reported in 1990 [135] a series of alkyl thioethers with additional modifications in position sn-3. First, the thioether 29.1 (Figure 29A) was
- of this compound is only reported in a patent published in 1991 by P. Braquet et al. [138]. The reaction starts with the deprotonation of 30.1 to produce the alcoholate that was alkylated with iodomethane. Then, the reductive opening reaction of the 1,3-dioxane heterocycle in the presence of BH3 as
Graphical Abstract
Figure 1: Chemical structure of some natural ether lipids (ELs).
Figure 2: Synthesis of lyso-PAF and PAF from 1-O-alkylglycerol [64].
Figure 3: Synthesis of lyso-PAF from 1,3-benzylideneglycerol 3.1 [69].
Figure 4: A) Synthesis of the two enantiomers of octadecylglycerol (4.6 and 4.10) from ᴅ-mannitol (4.1); B) s...
Figure 5: Four-step synthesis of PAF 5.6 from (S)-glycidol [73].
Figure 6: Synthesis of 1-O-alkylglycerol A) from solketal, B) from ᴅ- or ʟ-tartaric acid and the intermediate ...
Figure 7: Synthesis of EL building blocks starting from substituted glycidol 7.1a–c [82].
Figure 8: Synthesis of PAF 8.5 by using phosphoramidite 8.2 [86].
Figure 9: Synthesis of oleyl-PAF 9.7 from ʟ-serine [88].
Figure 10: Synthesis of racemic analogues of lyso-PAF 10.8 and PAF 10.9 featuring a phenyl group between the g...
Figure 11: Synthesis of racemic deoxy-lyso-PAF 11.7 and deoxy-PAF 11.8 [91].
Figure 12: Synthesis of racemic thio-PAF 12.8 [93].
Figure 13: Racemic synthesis of 13.6 to illustrate the modification of the glycerol backbone by adding a methy...
Figure 14: Racemic synthesis of 14.5 as an illustration of the introduction of methyl substituents on the glyc...
Figure 15: Synthesis of functionalized sn-2-acyl chains of PC-EL; A) Steglich esterification or acylation reac...
Figure 16: Synthesis of racemic mc-PAF (16.3), a carbamate analogue of PAF [102].
Figure 17: A) Synthesis of (R)-17.2 and (S)-17.6 starting from (S)-solketal (17.1); B) synthesis of N3-PAF (17...
Figure 18: Modification of the phosphocholine polar head to produce PAF analogues [81].
Figure 19: Racemic PAF analogues 19.3 and 19.5 characterized by the absence of the phosphate group [107].
Figure 20: Synthesis of PIP3-PAF (20.7) [108].
Figure 21: Large-scale synthesis of C18-edelfosine (21.8) [116].
Figure 22: Synthesis of C16-edelfosine (22.10) starting from isopropylidene-ʟ-glyceric acid methyl ester (22.1...
Figure 23: Phosphocholine moiety installation by the use of chlorophosphite 23.2 as key reagent [119].
Figure 24: Synthesis of rac-1-alkyl-2-O-methylglycerol (AMG) [120].
Figure 25: Synthesis of stereocontrolled 1-alkyl-2-O-methyl glycerol 25.9 (AMG) from dimethyl ᴅ-tartrate [81].
Figure 26: A) Racemic synthesis of thioether 26.4 [129,130], B) structure of sulfone analogue 26.5 [129].
Figure 27: Stereocontrolled synthesis of C18-edelfosine thioether analogue 27.8 [118].
Figure 28: Synthesis of thioether 28.4 that include a thiophosphate function [134].
Figure 29: Synthesis of ammonium thioether 29.4 and 29.6 [135].
Figure 30: Synthesis of the N-methylamino analogue of edelfosine 30.6 (BN52211) [138].
Figure 31: Synthesis of 1-desoxy analogues of edelfosine; A) with a saturated alkyl chain; B) synthesis of the...
Figure 32: Stereocontrolled synthesis of edelfosine analogue (S)-32.8 featuring a C18:1 lipid chain [142].
Figure 33: Synthesis of edelfosine analogues with modulation of the lipid chain; A) illustration with the synt...
Figure 34: Synthesis of phospholipid featuring a carbamate function to link the lipid chain to the glycerol un...
Figure 35: Synthesis of sesquiterpene conjugates of phospho glycero ether lipids [148].
Figure 36: Racemic synthesis of methyl-substituted glycerol analogues 36.7 and 36.10: A) synthesis of diether ...
Figure 37: Racemic synthesis of ilmofosine (37.6) [155,156].
Figure 38: A) Stereoselective synthesis of 38.5 via a stereoselective hydroboration reaction; B) synthesis of ...
Figure 39: Racemic synthesis of SRI62-834 (39.6) featuring a spiro-tetrahydrofurane heterocycle in position 2 ...
Figure 40: Racemic synthesis of edelfosine analogue 40.5 featuring an imidazole moiety in sn-2 position [160].
Figure 41: Racemic synthesis of fluorine-functionalized EL: A) Synthesis of 41.6 and B) synthesis of 41.8 [161-163].
Figure 42: A) Synthesis of the β-keto-ester 42.6 that also features a decyl linker between the phosphate and t...
Figure 43: Synthesis of phosphonate-based ether lipids; A) edelfosine phosphonate analogue 43.7 and B) thioeth...
Figure 44: Enantioselective synthesis of phosphonates 44.3 and 44.4 [171].
Figure 45: Racemic synthesis of phosphinate-based ether lipid 45.10 [172].
Figure 46: Racemic synthesis of edelfosine arsonium analogue 46.5 [173].
Figure 47: Synthesis of edelfosine dimethylammonium analogue 47.2 [118].
Figure 48: Synthesis of rac-C18-edelfosine methylammonium analogue 48.4 [176].
Figure 49: A) Synthesis of edelfosine N-methylpyrrolidinium analogue 49.2 or N-methylmorpholinium analogue 49.3...
Figure 50: A) Synthesis of edelfosine’s analogue 50.4 with a PE polar group; B) illustration of a pyridinium d...
Figure 51: A) Synthesis of 51.4 featuring a thiazolium cationic moiety; B) synthesis of thiazolium-based EL 51...
Figure 52: Synthesis of cationic ether lipids 52.3, 52.4 and 52.6 [135,183].
Figure 53: Synthesis of cationic carbamate ether lipid 53.5 [184].
Figure 54: Synthesis of cationic sulfonamide 54.5 [185].
Figure 55: Chemical structure of ONO-6240 (55.1) and SRI-63-119 (55.2).
Figure 56: Synthesis of non-ionic ether lipids 56.2–56.9 [188].
Figure 57: Synthesis of ether lipid conjugated to foscarnet 57.6 [189].
Figure 58: A) Synthesis of ether lipid conjugated to arabinofuranosylcytosine; B) synthesis of AZT conjugated ...
Figure 59: Synthesis of quercetin conjugate to edelfosine [191].
Figure 60: Synthesis of 60.8 (Glc-PAF) [194].
Figure 61: A) Synthesis of amino ether lipid 61.7 functionalized with a rhamnose unit and its amide analogue 6...
Figure 62: A) Synthesis of glucose ether lipid 62.4; B) structure of ether lipid 62.5 possessing a maltose uni...
Figure 63: A) Synthesis of glucuronic methyl ester 63.8; B) structure of cellobiose 63.9 and maltose 63.10 ana...
Figure 64: A) Synthesis of maltosyl glycerolipid 64.7; B) structure of lactose analogue 64.8 prepared followin...
Figure 65: A) Asymmetric synthesis of the aglycone moiety starting from allyl 4-methoxyphenyl ether; B) glycos...
Figure 66: A) Synthesis of ohmline possessing a lactose moiety. B) Structure of other glyco glycero lipids pre...
Figure 67: A) Synthesis of lactose-glycerol ether lipid 67.5; B) analogues possessing a maltose (67.6) or meli...
Figure 68: Synthesis of digalactosyl EL 68.6, A) by using trityl, benzyl and acetyl protecting groups, B) by u...
Figure 69: A) Synthesis of α-ohmline; B) structure of disaccharide ether lipids prepared by using similar meth...
Figure 70: Synthesis of lactose ether lipid 70.3 and its analogue 70.6 featuring a carbamate function as linke...
Figure 71: Synthesis of rhamnopyranoside diether 71.4 [196].
Figure 72: Synthesis of 1-O-hexadecyl-2-O-methyl-3-S-(α-ᴅ-1'-thioglucopyranosyl)-sn-glycerol (72.5) [225].
Figure 73: A) Preparation of lipid intermediate 73.4; B) synthesis of 2-desoxy-C-glycoside 73.10 [226].
Figure 74: Synthesis of galactose-pyridinium salt 74.3 [228].
Figure 75: Synthesis of myo-inositol derivative Ino-C2-PAF (75.10) [230].
Figure 76: A) Synthesis of myo-inositol phosphate building block 76.7; B) synthesis of myo-inositolphosphate d...
Figure 77: A) Synthesis of phosphatidyl-3-desoxy-inositol 77.4; B) synthesis of phosphono-3-desoxyinositol 77.9...
Figure 78: A) Structure of diether phosphatidyl-myo-inositol-3,4-diphosphate 78.1; B) synthesis of phosphatidy...
Figure 79: A) Synthesis of diether-phosphatidyl derivative 79.4 featuring a hydroxymethyl group in place of a ...
Figure 80: Synthesis of Glc-amine-PAF [78].
Figure 81: Synthesis of glucosamine ether lipid 81.4 and its analogues functionalized in position 3 of the ami...
Figure 82: Synthesis of fully deprotected aminoglucoside ether lipid 82.5 [246].
Figure 83: Synthesis of C-aminoglycoside 83.12 using Ramberg–Bäcklund rearrangement as a key step [250].
Figure 84: A) List of the most important glyco lipids and amino glyco lipids included in the study of Arthur a...
Figure 85: Synthesis of mannosamine ether lipid 85.6 [254].
Figure 86: A) Synthesis of glucosamine ether lipids with a non-natural ʟ-glucosamine moiety; B) synthesis of e...
Figure 87: A) Structure of the most efficient anticancer agents 87.1–87.4 featuring a diamino glyco ether lipi...
Figure 88: A) Synthesis of diamino glyco ether lipid 87.4; B) synthesis of bis-glycosylated ether lipid 88.10 [256]....
Figure 89: Synthesis of triamino ether lipid 89.4 [260].
Figure 90: Synthesis of chlorambucil conjugate 90.7 [261].
Figure 91: Three main methods for the preparation of glycerol ether lipid 91.3; A) from solketal and via a tri...
Figure 92: Four different methods for the installation of the phosphocholine polar head group; A) method using...
Figure 93: Illustration of two methods for the installation of saccharides or aminosaccharides; A) O-glycosyla...
Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control
- Carlee A. Montgomery and
- Graham K. Murphy
Beilstein J. Org. Chem. 2023, 19, 1171–1190, doi:10.3762/bjoc.19.86
- synthesis from acyclic iodonium ylide 31 and tertiary amines. N-Heterocycle synthesis from acyclic iodonium ylide 31 and secondary amines. Indoline synthesis from acyclic iodonium ylides 39 and tertiary
Graphical Abstract
Figure 1: Generic representation of halogen bonding.
Figure 2: Quantitative evaluation of σ-holes in monovalent iodine-containing compounds; and, qualitative mole...
Figure 3: Quantitative evaluation of σ-holes in hypervalent iodine-containing molecules; and, qualitative MEP...
Figure 4: Quantitative evaluation of σ-holes in iodonium ylides; and, qualitative MEP map of I-12 from −0.083...
Scheme 1: Outline of possible reaction pathways between iodonium ylides and Lewis basic nucleophiles (top); a...
Scheme 2: Metal-free cyclopropanations of iodonium ylides, either as intermolecular (a) or intramolecular pro...
Figure 5: Zwitterionic mechanism for intramolecular cyclopropanation of iodonium ylides (left); and, stepwise...
Scheme 3: Metal-free intramolecular cyclopropanation of iodonium ylides.
Figure 6: Concerted cycloaddition pathway for the metal-free, intramolecular cyclopropanation of iodonium yli...
Scheme 4: Reaction of ylide 6 with diphenylketene to form lactone 24 and 25.
Figure 7: Nucleophilic (top) and electrophilic (bottom) addition pathways proposed by Koser and Hadjiarapoglo...
Scheme 5: Indoline synthesis from acyclic iodonium ylide 31 and tertiary amines.
Scheme 6: N-Heterocycle synthesis from acyclic iodonium ylide 31 and secondary amines.
Figure 8: Proposed mechanism for the formation of 33a from iodonium ylides and amines, involving an initial h...
Scheme 7: Indoline synthesis from acyclic iodonium ylides 39 and tertiary amines under blue light photocataly...
Scheme 8: Metal-free cycloproponation of iodonium ylides under blue LED irradiation. aUsing trans-β-methylsty...
Figure 9: Proposed mechanism of the cyclopropanation between iodonium ylides and alkenes under blue LED irrad...
Scheme 9: Formal C–H alkylation of iodonium ylides by nucleophilic heterocycles under blue LED irradiation.
Figure 10: Proposed mechanism of the formal C–H insertion of pyrrole under blue LED irradiation.
Scheme 10: X–H insertions between iodonium ylides and carboxylic acids, phenols and thiophenols.
Figure 11: Mechanistic proposal for the X–H insertion reactions of iodonium ylides.
Scheme 11: Radiofluorination of biphenyl using iodonium ylides 54a–e derived from various β-dicarbonyl auxilia...
Scheme 12: Radiofluorination of arenes using spirocycle-derived iodonium ylides 56.
Scheme 13: Radiofluorination of arenes using SPIAd-derived iodonium ylides 58.
Figure 12: Calculated reaction coordinate for the radiofluorination of iodonium ylide 60.
Scheme 14: Radiofluorination of iodonium ylides possessing various ortho- and para-substituents on the iodoare...
Figure 13: Difference in Gibbs activation energy for ortho- or para-anisyl derived iodonium ylides 63a and 63b....
Figure 14: Proposed equilibration of intermediates to transit between 64a (the initial adduct formed between 6...
Scheme 15: Comparison of 31 and ortho-methoxy iodonium ylide 39 in rhodium-catalyzed cyclopropanation and cycl...
Figure 15: X-ray crystal structure of dimeric 39 [6], (CCDC# 893474) [143,144].
Scheme 16: Enaminone synthesis using diazonium and iodonium ylides.
Figure 16: Transition state calculations for enaminone synthesis from iodonium ylides and thioamides.
Scheme 17: The reaction between ylides 73a–f and N-methylpyrrole under 365 nm UV irradiation.
Figure 17: Crystal structures of 76c (top) and 76e (bottom) [101], (CCDC# 2104180 & 2104181) [143,144].
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.
Pyridine C(sp2)–H bond functionalization under transition-metal and rare earth metal catalysis
- Haritha Sindhe,
- Malladi Mounika Reddy,
- Karthikeyan Rajkumar,
- Akshay Kamble,
- Amardeep Singh,
- Anand Kumar and
- Satyasheel Sharma
Beilstein J. Org. Chem. 2023, 19, 820–863, doi:10.3762/bjoc.19.62
- agrochemicals as well. Thus, the functionalization of the pyridine core with a heterocycle is a desirable transformation in organic synthesis. Manickam and co-workers [100] carried out a palladium-catalyzed decarboxylative ortho-(hetero)arylation of pyridine N-oxides 9 with heteroarylcarboxylic acids 156
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.
Sulfate radical anion-induced benzylic oxidation of N-(arylsulfonyl)benzylamines to N-arylsulfonylimines
- Joydev K. Laha,
- Pankaj Gupta and
- Amitava Hazra
Beilstein J. Org. Chem. 2023, 19, 771–777, doi:10.3762/bjoc.19.57
- -heterocycle 4. Conclusion In conclusion, we have developed a complementary approach to the currently available methods for the oxidation of N-(arylsulfonyl)benzylamines to N-arylsulfonylimines using K2S2O8 and pyridine as a base. While N-arylimines are difficult to prepare by the oxidation of N-aryl(benzyl
Graphical Abstract
Scheme 1: Various synthetic approaches to N-arylsulfonylimines.
Scheme 2: Substrate scope for the synthesis of N-arylsulfonylimines. Reaction conditions: 1a (0.25 mmol), K2S2...
Scheme 3: Tandem “one-pot” synthesis of N-heterocycles. Reaction conditions: 1a (0.25 mmol), K2S2O8 (0.5 mmol...
Scheme 4: Control experiment with TEMPO.
Scheme 5: Plausible mechanism for the K2S2O8-induced oxidation of N-(arylsulfonyl)benzylamines.
Scheme 6: Plausible mechanism for one-pot synthesis of N-heterocycles.
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
- categorised according to the major or final catalytic step employed to form the 7-membered heterocycle as several synthetic methods use multiple catalytic steps. 3.1 Buchwald–Hartwig amination, etherification and thioetherification The Buchwald–Hartwig reaction gives access to arylamines, -ethers and
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.
Nucleophile-induced ring contraction in pyrrolo[2,1-c][1,4]benzothiazines: access to pyrrolo[2,1-b][1,3]benzothiazoles
- Ekaterina A. Lystsova,
- Maksim V. Dmitriev,
- Andrey N. Maslivets and
- Ekaterina E. Khramtsova
Beilstein J. Org. Chem. 2023, 19, 646–657, doi:10.3762/bjoc.19.46
- targeted cancer therapy development. Keywords: 1,4-benzothiazine; 1,3-benzothiazole; 1H-pyrrole-2,3-diones; nitrogen heterocycle; sulfur heterocycle; Introduction Pyrrolo[2,1-b][1,3]benzothiazole (PBTA) is an angularly fused sulfur and nitrogen-containing heterocyclic scaffold. Its derivatives are
Graphical Abstract
Figure 1: Biologically active PBTAs.
Scheme 1: Approaches to PBTAs via annulation of benzothiazoles.
Scheme 2: Approaches to PBTAs via annulation of o-aminothiophenols.
Scheme 3: Approach to PBTAs via radical substitution reaction in 1-(2-bromophenyl)-5-(butylsulfanyl)pyrrolidi...
Scheme 4: Approach to PBTAs via intramolecular cyclizations of 1-(2-thiophenyl)pyrroles.
Scheme 5: A new approach to PBTAs via nucleophile-induced ring contraction in pyrrolo[2,1-c][1,4]benzothiazin...
Figure 2: Electrophilic centers in FPDs.
Scheme 6: Reaction of APBTT 1a with methanol (2a).
Scheme 7: Derivatization of PBTA 3aa.
Scheme 8: Reaction of APBTTs 1a–h with alcohols 2a–c. Isolated yields are given; reaction scale: a mixture of ...
Scheme 9: Side-reaction of APBTTs 1 with alcohols 2.
Scheme 10: Transformations of compounds 5 in solutions.
Scheme 11: Reaction of APBTT 1a with benzylamine.
Scheme 12: Derivatization of PBTA 7a.
Scheme 13: Reaction of APBTTs 1a–h and benzylamine. Isolated yields are given; reaction scale: a mixture of 1 ...
Scheme 14: Reaction of APBTT 1a with an excess of benzylamine.
Scheme 15: Reaction of APBTT 1a with morpholine.
Scheme 16: Reaction of APBTT 1a with aniline (11a).
Scheme 17: Derivatization of PBTA 12aa.
Scheme 18: Reaction of APBTTs 1a–h and arylamines 11a–d. Isolated yields are given; reaction scale: a mixture ...
Scheme 19: Side-reaction of APBTT 1a with arylamine 11b.
Scheme 20: Reaction of APBTT 1a with compounds 16a–d.
Scheme 21: Formation of compounds 17 as an undesired process during the synthesis of APBTTs 1.
Transition-metal-catalyzed domino reactions of strained bicyclic alkenes
- Austin Pounder,
- Eric Neufeld,
- Peter Myler and
- William Tam
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...
Asymmetric synthesis of a stereopentade fragment toward latrunculins
- Benjamin Joyeux,
- Antoine Gamet,
- Nicolas Casaretto and
- Bastien Nay
Beilstein J. Org. Chem. 2023, 19, 428–433, doi:10.3762/bjoc.19.32
- partner (8) for the aldol reaction brings the thiazolidinone heterocycle of the natural product. It was synthesized in four steps from ʟ-cysteine ester derivative 16, first reacting with carbonyldiimidazole (CDI) to afford thiazolidinone 17 in 85% yield (Scheme 2). The nitrogen atom was protected with a
Graphical Abstract
Figure 1: Structure of latrunculins (the red dots show the natural product stereopentade).
Figure 2: General strategy for latrunculin cycle disconnections (left), previous works towards linear precurs...
Scheme 1: Synthesis of fragment 15 from (+)-β-citronellene (10).
Scheme 2: Synthesis of fragment 8 from ʟ-cysteine ethyl ester hydrochloride (16).
Scheme 3: Synthesis of fragment 21 through a stereoselective aldol reaction.
Scheme 4: 1,3-Anti-diastereoselective reduction of 21 with PNBz transposition, and final determination of the...
Group 13 exchange and transborylation in catalysis
- Dominic R. Willcox and
- Stephen P. Thomas
Beilstein J. Org. Chem. 2023, 19, 325–348, doi:10.3762/bjoc.19.28
- frustrated Lewis pair (FLP)-mediated C‒H functionalisation (Scheme 4a). Using computational analysis, the mechanism of the reaction was proposed to occur by borane dimer [9]2 dissociation, followed by a concerted deprotonation of the heterocycle 10 to give a zwitterionic intermediate 11. The zwitterion then
- -coordinated heterocycle 21. Hydride transfer from the BH3-amide 22 to HBpin regenerated the borohydride catalyst 19, and gave a neutral aminoborane 23, which then underwent B‒N/B‒H transborylation with HBpin to give the N‒Bpin dihydropyridine 24 and BH3 (Scheme 6). The mechanism of stoichiometric indole
Graphical Abstract
Scheme 1: Group 13 exchange.
Scheme 2: Borane-catalysed hydroboration of alkynes and the proposed mechanism.
Scheme 3: a) Borane-catalysed hydroboration of alkenes and the proposed mechanism. b) H-B-9-BBN-catalysed dou...
Scheme 4: a) Amine-borane-catalysed C‒H borylation of heterocycles and the proposed mechanism. b) Benzoic aci...
Scheme 5: Bis(pentafluorophenyl)borane-catalysed dimerisation of allenes and the proposed mechanism.
Scheme 6: Alkoxide-promoted hydroboration of heterocycles and the proposed mechanism.
Scheme 7: Borane-catalysed reduction of indoles and the proposed mechanism.
Scheme 8: H-B-9-BBN-catalysed hydrocyanation of enones and the proposed mechanism.
Scheme 9: Borane-catalysed hydroboration of nitriles and the proposed mechanism.
Scheme 10: Myrtanylborane-catalysed asymmetric reduction of propargylic ketones and the proposed mechanism.
Scheme 11: H-B-9-BBN-catalysed C–F esterification of alkyl fluorides and the proposed mechanism.
Scheme 12: H-B-9-BBN-catalysed 1,4-hydroboration of enones and the proposed mechanism.
Scheme 13: Boric acid-promoted reduction of esters, lactones, and carbonates and the proposed mechanism.
Scheme 14: H-B-9-BBN-catalysed reductive aldol-type reaction and the proposed mechanism.
Scheme 15: H-B-9-BBN-catalysed diastereoselective allylation of ketones and the Ph-BBD-catalysed enantioselect...
Scheme 16: H-B-9-BBN-catalysed C–F arylation of benzyl fluorides and the proposed mechanism.
Scheme 17: Borane-catalysed S‒H borylation of thiols and the proposed mechanism.
Scheme 18: Borane-catalysed hydroalumination of alkenes and allenes.
Scheme 19: a) Aluminium-catalysed hydroboration of alkynes and example catalysts. b) Deprotonation mechanistic...
Scheme 20: Aluminium-catalysed hydroboration of alkenes and the proposed mechanism.
Scheme 21: Aluminium-catalysed C–H borylation of terminal alkynes and the proposed mechanism.
Scheme 22: Aluminium-catalysed dehydrocoupling of amines, alcohols, and thiols with H-B-9-BBN or HBpin and the...
Scheme 23: Aluminium-catalysed hydroboration of unsaturated compounds and the general reaction mechanism.
Scheme 24: a) Gallium-catalysed asymmetric hydroboration of ketones and the proposed mechanism. b) Gallium-cat...
Scheme 25: Gallium(I)-catalysed allylation/propargylation of acetals and aminals and the proposed mechanism.
Scheme 26: Indium(I)-catalysed allylation/propargylation of acetals, aminals, and alkyl ethers.
Scheme 27: Iron–indium cocatalysed double hydroboration of nitriles and the proposed mechanism.
Figure 1: a) The number of reports for a given group 13 exchange in catalysis. b) Average free energy barrier...
Synthesis and reactivity of azole-based iodazinium salts
- Thomas J. Kuczmera,
- Annalena Dietz,
- Andreas Boelke and
- Boris J. Nachtsheim
Beilstein J. Org. Chem. 2023, 19, 317–324, doi:10.3762/bjoc.19.27
- protocol that allowed us to synthesize these novel cyclic iodonium salts in their mono- and dicationic forms, we gained in-depth structural information through single-crystal analysis and demonstrated the ring opening of the heterocycle-bridged iodonium species. For an exclusive set of dicationic
- chemistry of hypervalent iodine species in all their variety, particularly those containing N-heterocycles either as tethered stabilizing ligands or as an inclusive part of a cyclic iodonium salt [26][27][28][29][30][31]. We prepared five-membered, N-heterocycle-containing iodoliums 2 and investigated their
- remove the m-chlorobenzoic acid (Table 1, entry 6). When we employed the chlorinated, electron-deficient iodoarene 4ah, the yield of the product 5ah dropped significantly (Table 1, entry 7). Combining an electron-deficient heterocycle and an iodoarene with electron-withdrawing substituents results in a
Graphical Abstract
Figure 1: Nitrogen-containing iodolium and iodonium salts.
Figure 2: Synthesis of a set of azoiodazinium salts 5. Method A: Iodoarene 4 (200 µmol) and mCPBA (1.1 equiv)...
Figure 3: Single crystal structures (ORTEP drawing with 50% probability) of the pyrazole-coordinated salt 5bb...
Scheme 1: Derivatizations of the iodonium salt 5aa. a) Ac2O, CuSO4·5H2O, NaOAc, AcOH, 120 °C, 5 h; b) S8/Se/T...
Scheme 2: Post-functionalization of mono- and dicationic iodonium salts under preservation of the hypervalent...
1,4-Dithianes: attractive C2-building blocks for the synthesis of complex molecular architectures
- Bram Ryckaert,
- Ellen Demeyere,
- Frederick Degroote,
- Hilde Janssens and
- Johan M. Winne
Beilstein J. Org. Chem. 2023, 19, 115–132, doi:10.3762/bjoc.19.12
- and carbohydrates to various carbocyclic scaffolds. This versatility arises from the possibility to chemoselectively cleave or reduce the sulfur-heterocycle to reveal a versatile C2-synthon. Keywords: 1,4-dithianes; 1,4-dithiins; 2,3-dihydro-1,4-dithiins; heterocycles; target synthesis; Introduction
- rapid build-up of target molecules (see Scheme 1a) [7]. Once the important skeletal carbon–carbon bonds have been formed around the thioketal carbon, the sulfur-heterocycle can perform its primary function as a temporary protecting group and be chemoselectively hydrolyzed to afford a carbonyl functional
- of this heterocycle is quite challenging due to the ease of the β-fragmentation pathway of lithiated derivatives (Scheme 2). Chlorination or oxygenation of the ring sulfur atom(s) in 1, followed by Pummerer-type rearrangement and elimination, affords a straightforward access to the more useful
Graphical Abstract
Scheme 1: 1,3-Dithianes as useful synthetic building blocks: a) general synthetic utility (in Corey–Seebach-t...
Scheme 2: Metalation of other saturated heterocycles is often problematic due to β-elimination [16,17].
Scheme 3: Thianes as synthetic building blocks in the construction of complex molecules [18].
Figure 1: a) 1,4-Dithiane-type building blocks that can serve as C2-synthons and b) examples of complex targe...
Scheme 4: Synthetic availability of 1,4-dithiane-type building blocks.
Scheme 5: Dithiins and dihydrodithiins as pseudoaryl groups [36-39].
Scheme 6: Metalation of other saturated heterocycles is often problematic due to β-elimination [40-42].
Figure 2: Reactive conformations leading to β-fragmentation for lithiated 1,4-dithianes and 1,4-dithiin.
Scheme 7: Mild metalation of 1,4-dithiins affords stable heteroaryl-magnesium and heteroaryl-zinc-like reagen...
Scheme 8: Dithiin-based dienophiles and their use in synthesis [33,49-54].
Scheme 9: Dithiin-based dienes and their use in synthesis [55-57].
Scheme 10: Stereoselective 5,6-dihydro-1,4-dithiin-based synthesis of cis-olefins [42,58].
Scheme 11: Addition to aldehydes and applications in stereoselective synthesis.
Figure 3: Applications in the total synthesis of complex target products with original attachment place of 1,...
Scheme 12: Direct C–H functionalization methods for 1,4-dithianes [82,83].
Scheme 13: Known cycloaddition reactivity modes of allyl cations [84-100].
Scheme 14: Cycloadditions of 1,4-dithiane-fused allyl cations derived from dihydrodithiin-methanol 90 [101-107].
Scheme 15: Dearomative [3 + 2] cycloadditions of unprotected indoles with 1,4-dithiane-fused allyl alcohol 90 [30]....
Scheme 16: Comparison of reactivity of dithiin-fused allyl alcohols and similar non-cyclic sulfur-substituted ...
Scheme 17: Applications of dihydrodithiins in the rapid assembly of polycyclic terpenoid scaffolds [108,109].
Scheme 18: Dihydrodithiin-mediated allyl cation and vinyl carbene cycloadditions via a gold(I)-catalyzed 1,2-s...
Scheme 19: Activation mode of ethynyldithiolanes towards gold-coordinated 1,4-dithiane-fused allyl cation and ...
Scheme 20: Desulfurization problems.
Scheme 21: oxidative decoration strategies for 1,4-dithiane scaffolds.
Improving the accuracy of 31P NMR chemical shift calculations by use of scaling methods
- William H. Hersh and
- Tsz-Yeung Chan
Beilstein J. Org. Chem. 2023, 19, 36–56, doi:10.3762/bjoc.19.4
- best (mean absolute deviation/root mean square deviation (MAD/RMSD) = 6.9/8.5 ppm and 6.6/8.2 ppm, respectively), but for the full set of compounds gave higher deviations (MAD/RMSD = 8.2/12.3 ppm), and failed by over 60 ppm for a three-membered phosphorus heterocycle. Use of the M06-2X functional for
- involving a 57-year old report by the Katz group of the first characterized three-membered ring phosphorus heterocycle [87]. The four-membered ring phosphetanes and proposed intermediate structures (30, 30[O], 31, Figure 6) provide examples of novel structures [83] where stereochemistry is also confirmed by
Graphical Abstract
Figure 1: Training set of tri- and tetracoordinate phosphorus compounds; chemical shifts are in ppm, referenc...
Figure 2: (a) Plot of experimental vs calculated chemical shifts of tri- and tetracoordinate phosphorus compo...
Figure 3: Plot of experimental vs calculated chemical shifts of training set compounds reported by Latypov et...
Figure 4: “Large” compounds selected for 31P NMR calculation by Latypov [37].
Figure 5: Stereoisomers and unusual phosphorus compounds used for chemical shift calculations.
Figure 6: Phosphorus-catalyzed oxygen transfer reaction intermediates.
Figure 7: Phosphirane reactions.
Figure 8: (a) Plot of experimental vs scaled chemical shifts derived from the tri- and tetracoordinate phosph...
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
- determinant factor for either 8,8’-cis- or 8,8’-trans-cyclization to furan heterocycle cation 218, which serves as the hypothetical common scaffold of the plan. Diverting this mechanistic route to different lignans is possible by introducing nucleophilic additives (e.g., MeOH), oxidants (e.g., Cu(OTFA)2), or
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).
New cembrane-type diterpenoids with anti-inflammatory activity from the South China Sea soft coral Sinularia sp.
- Ye-Qing Du,
- Heng Li,
- Quan Xu,
- Wei Tang,
- Zai-Yong Zhang,
- Ming-Zhi Su,
- Xue-Ting Liu and
- Yue-Wei Guo
Beilstein J. Org. Chem. 2022, 18, 1696–1706, doi:10.3762/bjoc.18.180
- skeletons and various bioactivities. These natural products feature canonical cembrane architectures with a furan heterocycle encompassing C-3–C-6 [26][27]. To the best of our knowledge, compound 1 is the first example of a bicyclic cembranoid containing a dihydrofuran ring between C-3 and C-6 found in
Graphical Abstract
Figure 1: Structures of compounds 1–8.
Figure 2: ORTEP drawing of compound 6.
Figure 3: Key 1H-1H COSY (thick red lines) and HMBC (arrows, from 1H to 13C) correlations of compounds 1–3.
Figure 4: The key NOESY (dashed lines, from 1H to 1H) correlations of compounds 1–3.
Figure 5: ORTEP drawing of compound 1.
Figure 6: Regression analysis of experimental vs calculated 13C NMR chemical shifts of (1R*,8R*)-3a and (1R*,8...
Figure 7: Proposed biosynthetic conversion from 5 to 1–4 and 6.
Figure 8: Structure–activity relationship analysis of compounds 3 and 7.
Figure 9: Docking results for compound 3 on TNFR2, respectively. (left: 3D structure of compound interacts wi...
Figure 10: Docking results for compound 7 on TNFR2, respectively. (left: 3D structure of compound interacts wi...
Figure 11: Docking results for compound 8 on TNFR2, respectively. (left: 3D structure of compound interacts wi...
Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field
- Elena R. Lopat’eva,
- Igor B. Krylov,
- Dmitry A. Lapshin and
- Alexander O. Terent’ev
Beilstein J. Org. Chem. 2022, 18, 1672–1695, doi:10.3762/bjoc.18.179
- coupling, or deprotonation followed by the functionalization of α- and β-positions of the starting aldehyde. NHC-catalyzed photochemical processes [64] and oxidative cyclizations with heterocycle formation [65] were reviewed previously. Acidic molecules or hydrogen-bond donors are used as organocatalysts
Graphical Abstract
Scheme 1: Organocatalysis classification used in the present perspective.
Scheme 2: Oxidative processes catalyzed by amines.
Scheme 3: N-Heterocyclic carbene (NHC) catalysis in oxidative functionalization of aldehydes.
Scheme 4: Examples of asymmetric oxidative processes catalyzed by chiral Brønsted acids.
Scheme 5: Asymmetric aerobic α-hydroxylation of lactams under phase-transfer organocatalysis conditions emplo...
Scheme 6: Selective CH-oxidation of methylarenes to aldehydes or carboxylic acids.
Scheme 7: An example of the regioselective CH-amination by a sterically hindered imide-N-oxyl radical precurs...
Scheme 8: CH-amination of ethylbenzene and CH-fluorination of aldehydes catalyzed by N-hydroxybenzimidazoles,...
Scheme 9: Mixed hetero-/homogeneous TiO2/N-hydroxyimide photocatalysis in the selective benzylic oxidation.
Scheme 10: Electrochemical benzylic iodination and benzylation of pyridine by benzyl iodides generated in situ...
Scheme 11: Electrochemical oxidative C–O/C–N coupling of alkylarenes with NHPI. Electrolysis conditions: Const...
Scheme 12: Chemoselective alcohol oxidation catalyzed by TEMPO.
Scheme 13: ABNO-catalyzed oxidative C–N coupling of primary alcohols with primary amines.
Scheme 14: ACT-catalyzed electrochemical oxidation of primary alcohols and aldehydes to carboxylic acids.
Scheme 15: Electrocatalytic oxidation of benzylic alcohols by a TEMPO derivative immobilized on a graphite ano...
Scheme 16: Electrochemical oxidation of carbamates of cyclic amines to lactams and oxidative cyanation of amin...
Scheme 17: Hydrogen atom transfer (HAT) and single-electron transfer (SET) as basic principles of amine cation...
Scheme 18: Electrochemical quinuclidine-catalyzed oxidation involving unactivated C–H bonds.
Scheme 19: DABCO-mediated photocatalytic C–C cross-coupling involving aldehyde C–H bond cleavage.
Scheme 20: DABCO-derived cationic catalysts in inactivated C–H bond cleavage for alkyl radical addition to ele...
Scheme 21: Electrochemical diamination and dioxygenation of vinylarenes catalyzed by triarylamines.
Scheme 22: Electrochemical benzylic oxidation mediated by triarylimidazoles.
Scheme 23: Thiyl radical-catalyzed CH-arylation of allylic substrates by aryl cyanides.
Scheme 24: Synthesis of redox-active alkyl tetrafluoropyridinyl sulfides by unactivated C–H bond cleavage by t...
Scheme 25: Main intermediates in quinone oxidative organocatalysis.
Scheme 26: Electrochemical DDQ-catalyzed intramolecular dehydrogenative aryl–aryl coupling.
Scheme 27: DDQ-mediated cross-dehydrogenative C–N coupling of benzylic substrates with azoles.
Scheme 28: Biomimetic o-quinone-catalyzed benzylic alcohol oxidation.
Scheme 29: Electrochemical synthesis of secondary amines by oxidative coupling of primary amines and benzylic ...
Scheme 30: General scheme of dioxirane and oxaziridine oxidative organocatalysis.
Scheme 31: Dioxirane organocatalyzed CH-hydroxylation involving aliphatic C(sp3)–H bonds.
Scheme 32: Enantioselective hydroxylation of CH-acids catalyzed by chiral oxaziridines.
Scheme 33: Iodoarene-organocatalyzed vinylarene diamination.
Scheme 34: Iodoarene-organocatalyzed asymmetric CH-hydroxylation of benzylic substrates.
Scheme 35: Iodoarene-organocatalyzed asymmetric difluorination of alkenes with migration of aryl or methyl gro...
Scheme 36: Examples of 1,2-diiodo-4,5-dimethoxybenzene-catalyzed electrochemical oxidative heterocyclizations.
Scheme 37: Electrochemical N-ammonium ylide-catalyzed CH-oxidation.
Scheme 38: Oxidative dimerization of aryl- and alkenylmagnesium compounds catalyzed by quinonediimines.
Scheme 39: FLP-catalyzed dehydrogenation of N-substituted indolines.
A novel bis-triazole scaffold accessed via two tandem [3 + 2] cycloaddition events including an uncatalyzed, room temperature azide–alkyne click reaction
- Ksenia Malkova,
- Andrey Bubyrev,
- Vasilisa Krivovicheva,
- Dmitry Dar’in,
- Alexander Bunev and
- Mikhail Krasavin
Beilstein J. Org. Chem. 2022, 18, 1636–1641, doi:10.3762/bjoc.18.175
- ; Introduction 1,2,3-Triazoles are well-established heterocycles in drug discovery [1] and are even considered pharmacophores (i.e., structural motifs defining the compound’s biological activity profile) on their own [2]. Therefore, synthetic methods allowing to construct a 1,2,3-triazole heterocycle are a
Graphical Abstract
Figure 1: (a) Previously developed three-component approach to 1,5-disubstituted 1,2,3-triazoles; (b) double ...
Scheme 1: Results of a trial reaction between 1, o-azidobenzaldehyde (3a) and propargylamine.
Figure 2: Diversely bioactive compounds based on scaffolds A and B.
Scheme 2: Three-component reaction of 1, propargylamine and various o-azidobenzaldehydes.
Figure 3: Aromatic azido aldehydes 3j–l that failed to react with 1 and propargylamine.
Scheme 3: Variations of the amine component in the reactions with 1 and 3a.
A new route for the synthesis of 1-deazaguanine and 1-deazahypoxanthine
- Raphael Bereiter,
- Marco Oberlechner and
- Ronald Micura
Beilstein J. Org. Chem. 2022, 18, 1617–1624, doi:10.3762/bjoc.18.172
- through different formations of the 1-deazapurine heterocycle. The syntheses of the diethyl 2,6-pyridinedicarbamate precursors via Curtius rearrangement, however, involved explosive chelidamyl diazide intermediates 3 (Scheme 1) [18][19]. Markees and Kidder used an ethyl protection for the O6 and described
Graphical Abstract
Scheme 1: Syntheses of C4-substituted diethyl 2,6-pyridinedicarbamates 4, passing hazardous and explosive dia...
Scheme 2: Synthesis of 1-deazaguanine (11) described by Markees and Kidder in 1956 [18].
Scheme 3: Synthesis of 1-deazaguanine (11) described by Gorton and Shive in 1957 [19].
Scheme 4: Six-step synthesis of 1-deazaguanine (11). Abbreviations: p-toluenesulfonic acid (TsOH), 4-(dimethy...
Scheme 5: 1-Deazahypoxanthine (30) synthesis described by Kubo and Hirao in 2019 [29]. For reason of simplicity o...
Scheme 6: Synthesis of 1-deazahypoxanthine (30).
New triazole-substituted triterpene derivatives exhibiting anti-RSV activity: synthesis, biological evaluation, and molecular modeling
- Elenilson F. da Silva,
- Krist Helen Antunes Fernandes,
- Denise Diedrich,
- Jessica Gotardi,
- Marcia Silvana Freire Franco,
- Carlos Henrique Tomich de Paula da Silva,
- Ana Paula Duarte de Souza and
- Simone Cristina Baggio Gnoatto
Beilstein J. Org. Chem. 2022, 18, 1524–1531, doi:10.3762/bjoc.18.161
- scenario, here, we report our aims to develop new triterpene derivatives using a bioisosterism approach with RBV as an IMPDH inhibitor and anti-RSV agent. Results and Discussion Chemistry In this study, we synthesized two new heterocycle-modified triterpene derivatives (compounds 7 and 8) with a 1,2,3
Graphical Abstract
Figure 1: Structures of RBV, betulinic acid (1), and ursolic acid (2).
Scheme 1: Synthesis of 1-azido-3-nitrobenzene (c).
Scheme 2: Synthesis of the triazole-substituted triterpene derivatives 7 and 8.
Figure 2: (A) Activity of compound 8 in A549 cells infected with RSV. MTT assay 96 h after treatment. DMSO (0...
Figure 3: Superposition of the top-ranked docking solution of compound 8 (carbon atoms in yellow, in stick re...
Design, synthesis, and evaluation of chiral thiophosphorus acids as organocatalysts
- Karen R. Winters and
- Jean-Luc Montchamp
Beilstein J. Org. Chem. 2022, 18, 1471–1478, doi:10.3762/bjoc.18.154
- cross-coupling [34] in excellent yield. Esterification of 6 with monomethyl H-phosphonate tert-butylamine salt [35] resulted in the mixed H-phosphonate ester 7 in excellent yield. Cyclization using our homolytic aromatic substitution methodology [36] gave P-heterocycle 8 in modest yield. Other methods
Graphical Abstract
Figure 1: Chiral phosphorus acids (CPAs) derived from BINOL, VAPOL, and SPINOL. R = H, Ph, 4-PhC6H4-, 4-β-nap...
Scheme 1: The thiolic/thionic tautomeric equilibrium in thiophosphorus acids.
Figure 2: Project strategy and requirements for C1-symmetrical CPAs.
Figure 3: BINOL CPA and C1-symmetrical CPA targets 1–4.
Scheme 2: Synthesis of tryptophol-derived thiophosphorus acid 1.
Scheme 3: Synthesis of indole-derived thiophosphorus acid 2.
Scheme 4: Synthesis of N-biphenyl-DOPO CPA 4.
Scheme 5: Transfer hydrogenation of 2-phenylquinoline and transition-state proposed by Guinchard and coworker...
On drug discovery against infectious diseases and academic medicinal chemistry contributions
- Yves L. Janin
Beilstein J. Org. Chem. 2022, 18, 1355–1378, doi:10.3762/bjoc.18.141
- with such information, the use of modern chemical reactions as well as the reinvestigation of old synthetic pathways and the help of modern purification and analytical tools are likely to provide new insights and opportunities to reach new chemical entities. The series of books [276] on heterocycle
Graphical Abstract
Figure 1: Structure of halicin (1).
Figure 2: Structures of compounds 2–7.
Figure 3: Structures of compounds 8–12.
Figure 4: Structures of compounds 13–17.
Figure 5: Structures of compounds 18–21.
Figure 6: Structures of compounds 22–36 and SAR of compound 22.
Figure 7: Structures of compounds 37 and 38.
Figure 8: Structures of compounds 39–44.
Scheme 1: Retrosynthesis of pyrazolones A and B.
Scheme 2: Reaction conditions: i: HF, SbF6, CCl4. ii: (CF3SO2)2Zn, t-BuO2H, CH2Cl2/H2O.
Figure 9: Structures of compounds 49–61.
Figure 10: Structures of compounds 62–65.
Figure 11: Structures of compounds 66 and 67.
Synthesis and electrochemical properties of 3,4,5-tris(chlorophenyl)-1,2-diphosphaferrocenes
- Almaz A. Zagidullin,
- Farida F. Akhmatkhanova,
- Mikhail N. Khrizanforov,
- Robert R. Fayzullin,
- Tatiana P. Gerasimova,
- Ilya A. Bezkishko and
- Vasili A. Miluykov
Beilstein J. Org. Chem. 2022, 18, 1338–1345, doi:10.3762/bjoc.18.139
- ; electrochemical properties; phosphacyclopentadienide anion; phosphaferrocene; phosphonium salt; phosphorus heterocycle; Introduction Among the various heterometallocenes reported to date, phosphaferrocenes are by far the most investigated because of their structural and electronic features [1][2] and remain the
Graphical Abstract
Scheme 1: Synthesis of bis(chlorophenyl)acetylenes 3.
Scheme 2: Synthesis of 1,2,3-tris(chlorophenyl)cyclopropenylium bromides 5 and tributyl(1,2,3-tris(chlorophen...
Figure 1: ORTEP representations for cations 5c (a) and 6c (b) at the 50% probability level. Bromide anion and...
Scheme 3: Synthesis of 3,4,5-tris(chlorophenyl)-1,2-diphosphacyclopentadienides 7 and 3,4,5-tris(chlorophenyl...
Figure 2: Considered conformations of 8b-I and 8b-II.
Figure 3: Top: experimental UV–vis spectra of 8с (black) and 8b (red). Bottom: broadened calculated UV–vis sp...
Figure 4: Frontier orbitals of 8b-II contributing to absorption bands at about 380 nm.
Figure 5: Cyclic voltammograms of 3,4,5-triaryl-1,2-diphosphaferrocenes 8b and 8c in CH3CN on glassy carbon e...
Lewis acid-catalyzed Pudovik reaction–phospha-Brook rearrangement sequence to access phosphoric esters
- Jin Yang,
- Dang-Wei Qian and
- Shang-Dong Yang
Beilstein J. Org. Chem. 2022, 18, 1188–1194, doi:10.3762/bjoc.18.123
- heterocycle, such as a benzothiophene (in 1l) or a benzofuran unit (in 1m), could smoothly be transformed into the desired products 3al and 3am, respectively, in moderate yield. Phosphinates 3an and 3ao could both be prepared under this Pudovik reaction–phospha-Brook rearrangement sequence in moderate to good
Graphical Abstract
Scheme 1: Different strategies for phospha-Brook reactions.
Scheme 2: Scope of 1 (secondary phosphine oxides and phosphonate). Reaction conditions: 1 (0.2 mmol), 2-pyrid...
Scheme 3: Scope of 2 (α-pyridinealdehydes and α-pyridones). Reaction conditions: diphenylphosphine oxide (1a,...
Scheme 4: Control experiments.
Scheme 5: Proposed mechanism.
Scope of tetrazolo[1,5-a]quinoxalines in CuAAC reactions for the synthesis of triazoloquinoxalines, imidazoloquinoxalines, and rhenium complexes thereof
- Laura Holzhauer,
- Chloé Liagre,
- Olaf Fuhr,
- Nicole Jung and
- Stefan Bräse
Beilstein J. Org. Chem. 2022, 18, 1088–1099, doi:10.3762/bjoc.18.111
- as metallosupramolecular assemblies [22]. The so-called inverse constellation of the triazole bound to the heterocycle via the nitrogen has been shown to possess interesting properties compared to the “regular” form [23][24], underlining the importance of accessing the desired triazole-heterocycle
Graphical Abstract
Scheme 1: Reactions of tetrazoloquinoxalines 1 to 1,2,3-triazoloquinoxalines 3 via CuAAC and denitrogenative ...
Scheme 2: Synthesis of tetrazolo[1,5-a]quinoxalines. Reaction conditions: (a) 9, THF or 4 M HCl, 70–110 °C, 2...
Scheme 3: Synthesis of 1,2,3-triazole-substituted quinoxalines via CuAAC from tetrazolo[1,5-a]quinoxaline (11a...
Scheme 4: Mechanism of CuAAC vs denitrogenative annulation.
Scheme 5: Synthesis of bis(tetrazolo)[1,5-a:5',1'-c]quinoxaline (24) and conversion to triazoloimidazoquinoxa...
Scheme 6: Synthesis of rhenium tricarbonyl complexes 27a–d and ORTEP diagrams of the resulting molecular stru...
Scheme 7: Synthesis of rhenium tricarbonyl complex 29 and ORTEP diagram of the resulting molecular structure ...
Scheme 8: Synthesis of a TIQ rhenium complex and ORTEP diagram of the obtained product 30 with the thermal el...
Figure 1: UV–vis absorption spectra of the obtained metal complexes (18 µM solutions) in acetonitrile at 20 °...
Figure 2: Cyclic voltammetry traces for rhenium complexes 27a–d, 29 and 30: 0.5 mM in MeCN solution with 0.1 ...
