Rhodium(III)-Catalyzed Annulative Coupling of Sulfoxonium Ylides and Allenoates: An Arene C–H Activation/Cyclopropanation Cascade

Organic Letters, Journal Year: 2019, Volume and Issue: 21(22), P. 9217 - 9222

Published: Nov. 5, 2019

Rhodium(III)-catalyzed annulative coupling of sulfoxonium ylides with allenoates was achieved, forming highly functionalized cyclopropanes a quaternary carbon center by means the ylide functionality as traceless bifunctional directing group and C4 synthon via an arene C–H activation cyclopropanation cascade. The protocol features simultaneous formation three new C–C bonds in one pot excellent diastereoselectivity. resultant products could be further transformed to diverse synthetically useful compounds.

Language: Английский

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Rh(III)-Catalyzed Reaction of α-Carbonyl Sulfoxonium Ylides and Alkenes: Synthesis of Indanones via [4 + 1] Cycloaddition

Organic Letters, Journal Year: 2020, Volume and Issue: 22(4), P. 1375 - 1379

Published: Feb. 3, 2020

The synthesis of indanone derivatives by the Rh(III)-catalyzed reaction α-carbonyl sulfoxonium ylides with activated alkenes is reported. shows a high tolerance for functional groups and furnishes variety substituted via formal [4 + 1] cycloaddition. Highly stable were used as substrates in this C-H functionalization, their bifunctional character could be effectively exploited using Rh(III) catalysis sequential double C-C bond formation. Based on mechanistic studies including deuterium-labeling experiments, proposed to proceed follows: oxidative alkenylation β-hydride elimination, readdition H-Rh species, 1,2-carbon shift elimination DMSO, protonation.

Language: Английский

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Deacylation-aided C–H alkylative annulation through C–C cleavage of unstrained ketones

Nature Catalysis, Journal Year: 2021, Volume and Issue: 4(8), P. 703 - 710

Published: Aug. 2, 2021

Language: Английский

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Ruthenium-Catalyzed Chemoselective N–H Bond Insertion Reactions of 2-Pyridones/7-Azaindoles with Sulfoxonium Ylides

Organic Letters, Journal Year: 2021, Volume and Issue: 23(3), P. 1038 - 1043

Published: Jan. 21, 2021

A ruthenium-catalyzed highly chemoselective N-alkylation of 2-pyridones has been developed, affording N-alkylated 2-pyridone derivatives in good yields and excellent N-selectivity. The key to achieve this unprecedented N–H rather than O–H insertion reaction is the use CpRu(PPh3)2Cl as catalyst sulfoxonium ylides alkylation reagents. Moreover, protocol also amenable 7-azaindoles by slightly varying conditions. Furthermore, sulfonium are suitable reagents, providing selectivity.

Language: Английский

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Transition-Metal-, Additive-, and Solvent-Free [3 + 3] Annulation of RCF₂-Imidoyl Sulfoxonium Ylides with Cyclopropenones to Give Multifunctionalized CF₃-Pyridones

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 87(2), P. 1124 - 1132

Published: Dec. 29, 2021

An efficient and practical strategy was developed to synthesize 1,3,4-triaryl-6-trifluoromethylpyridones from CF3-imidoyl sulfoxonium ylides cyclopropenones in good excellent yields. This stepwise [3 + 3] annulation reaction carried out under transition-metal-, additive-, solvent-free conditions, generating 1 equiv of dimethyl sulfoxide as byproduct tolerating a series functional groups.

Language: Английский

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Recent Advances in Visible‐Light‐Driven C−S Bond Formation

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(20), P. 3413 - 3431

Published: Sept. 12, 2023

Abstract Due their multifaced applications, the access to organosulfur derivatives in an efficient and economical way is a challenge organic synthesis. In this context photochemistry photocatalysis play crucial role development of innovative (and selective) Carbon‐Sulphur bond formation processes. The present review aims collect most recent strategies achieve target under visible light driven conditions.

Language: Английский

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Electrochemical Selenylation of Sulfoxonium Ylides for the Synthesis of gem-Diselenides as Antimicrobials against Fungi

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(9), P. 5572 - 5585

Published: April 21, 2023

Organoselenium compounds are important scaffolds in pharmaceutical molecules. Herein, we report metal-free, electrochemical, highly chemo- and regioselective synthesis of gem-diselenides through the coupling α-keto sulfoxonium ylides with diselenides. The versatility electrochemical manifold enabled selenylation ample scope broad functional group tolerance, as well setting stage for modification complex bioactive Detailed mechanistic studies revealed that key C-Se bond was constructed using n-Bu4NI an electrolyte catalyst electrosynthetic protocol. Finally, desired showed excellent antimicrobial activity against Candida albicans, which can be identified lead further exploration.

Language: Английский

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High‐Throughput Experimentation and Machine Learning‐Assisted Optimization of Iridium‐Catalyzed Cross‐Dimerization of Sulfoxonium Ylides

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(48)

Published: Oct. 10, 2023

A novel and convenient approach that combines high-throughput experimentation (HTE) with machine learning (ML) technologies to achieve the first selective cross-dimerization of sulfoxonium ylides via iridium catalysis is presented. variety valuable amide-, ketone-, ester-, N-heterocycle-substituted unsymmetrical E-alkenes are synthesized in good yields high stereoselectivities. This mild method avoids use diazo compounds characterized by simple operation, step-economy, excellent chemoselectivity functional group compatibility. The combined experimental computational studies identify an amide-sulfoxonium ylide as a carbene precursor. Furthermore, comprehensive exploration reaction space also performed (600 reactions) model for yield prediction has been constructed.

Language: Английский

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HTE and machine learning-assisted development of iridium(i)-catalyzed selective O–H bond insertion reactions toward carboxymethyl ketones

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(5), P. 1153 - 1159

Published: Jan. 1, 2023

By combining HTE and machine learning technologies, an iridium( i )-catalyzed highly selective O–H bond insertion reaction of carboxylic acids sulfoxonium ylides was developed, extensive space exploration accomplished.

Language: Английский

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Recent advances in the synthesis of bridgehead (or ring-junction) nitrogen heterocycles via transition metal-catalyzed C–H bond activation and functionalization

Organic Chemistry Frontiers, Journal Year: 2020, Volume and Issue: 7(19), P. 3067 - 3099

Published: Jan. 1, 2020

An update on recent advances in the synthesis of bridgehead nitrogen fused heterocycles via transition metal-catalyzed C–H activation and functionalization is reported.

Language: Английский

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