Catalytic Asymmetric C–H Activation/Cyclization of Sulfoximines with Sulfoxonium Ylides by a Chiral η⁶-Benzene Ruthenium(II) Catalyst

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17398 - 17404

Published: Nov. 12, 2024

Chiral η6-benzene ruthenium(II) (BenRuII)-catalyzed asymmetric C–H activations are challenging and rarely seen in the literature. Herein, activation/cyclization of sulfoximines with sulfoxonium ylides catalyzed by chiral BenRuII catalyst derived from (S)-H8–BINOL is described. It provides efficient access to various sulfur-chiral 1,2-benzothiazine 1-oxides high yields enantioselectivities (up 99% yield 98% ee). Kinetic resolution racemic was also feasible. The reaction mechanism studied tool H/D exchange kinetic isotope effect. metallacycle revealing origin induction prepared, characterized, proved effective for model reaction. This work demonstrates great potential catalysts activation.

Language: Английский

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Ruthenium(II)-Catalyzed Construction of Isocoumarins via Dual C–H/C–C Activation of Sulfoxonium Ylides

The Journal of Organic Chemistry, Journal Year: 2019, Volume and Issue: 85(2), P. 1216 - 1223

Published: Dec. 6, 2019

A ruthenium(II)-catalyzed annulation between two molecules of sulfoxonium ylides is achieved, generating a variety substituted isocoumarins in reasonable yields. This strategy features dual C–H/C–C activation one pot and has wide substrate scope good functional group tolerance.

Language: Английский

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Rh(iii)-Catalyzed sequential ortho-C–H oxidative arylation/cyclization of sulfoxonium ylides with quinones toward 2-hydroxy-dibenzo[b,d]pyran-6-ones

Chemical Communications, Journal Year: 2020, Volume and Issue: 56(49), P. 6688 - 6691

Published: Jan. 1, 2020

A rhodium(iii)-catalyzed ortho-C-H functionalization of sulfoxonium ylides followed by intramolecular annulation reactions with quinones was described, where the carbonyl in served as a chelation group. This protocol leads to efficient formation 2-hydroxy-6H-benzo[c]chromen-6-one derivatives, proceeding cleavage C(O)-S bond ylides. featured high chemo-selectivity and functional group tolerance, acted aroyl sources.

Language: Английский

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Mn(III)-Mediated Radical Cyclization of o-Alkenyl Aromatic Isocyanides with Boronic Acids: Access to N-Unprotected 2-Aryl-3-cyanoindoles

Organic Letters, Journal Year: 2021, Volume and Issue: 23(15), P. 5826 - 5830

Published: July 29, 2021

The synthesis of N-unprotected 2-aryl-3-cyanoindoles was realized via the Mn(III)-mediated radical cascade cyclization o-alkenyl aromatic isocyanides with boronic acids. A possible mechanism involving a sequential intermolecular addition, intramolecular cyclization, and cleavage C–C bond under mild reaction conditions is proposed. Mechanism studies show that H2O or O2 might provide oxygen source for elimination benzaldehyde.

Language: Английский

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Rh(III)‐Catalyzed Diverse C—H Functionalization of Iminopyridinium Ylides

Chinese Journal of Chemistry, Journal Year: 2021, Volume and Issue: 39(9), P. 2489 - 2494

Published: May 9, 2021

Main observation and conclusion Divergent synthesis of useful skeletons has been realized via rhodium(III)‐catalyzed C—H activation iminopyridinium ylides coupling with various unsaturated reagents. Isocoumarins isoquinolones were obtained cleavage the C—N or N—N bond in ylidic directing group, while fluorinated alkenes delivered group intact. The reactions occurred wide substrate scopes good efficiency under redox‐neutral air‐tolerant conditions. Representative products exhibit solid‐state fluorescent property bioactivity inhibition toward human cancer cells.

Language: Английский

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Cobalt(III)-Catalyzed Chemo- and Regioselective [4 + 2]-Annulation of Aromatic Sulfoxonium Ylides with 1,3-Diynes

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(6), P. 4134 - 4153

Published: March 4, 2022

Air-stable, highly abundant, and cost-effective Co(III)-catalyzed redox-neutral [4 + 2]-annulation of aromatic sulfoxonium ylides with 1,3-diynes providing useful substituted 1-naphthol derivatives in a regioselective manner is described. Further, the prepared 1-naphthols having internal alkyne were converted into polycarbocyclic molecules spiro-dienone good-to-excellent yields. A possible reaction mechanism involving ortho C–H activation as key step was proposed supported by deuterium labeling kinetic isotope studies.

Language: Английский

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α-Carbonyl sulfoxonium ylides in transition metal-catalyzed C–H activation: a safe carbene precursor and a weak directing group

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 21(5), P. 879 - 909

Published: Dec. 6, 2022

Transition metal-catalyzed cross-coupling of sp2 C-H bonds with diazo compounds via carbene migratory insertion represents an efficient strategy for the construction C-C and C-heteroatom in organic synthesis. Despite popularity as coupling partners activation, they pose serious safety stability issues due to potential exothermic reactions linked release N2 gas. However, compared compounds, sulfoxonium ylides are generally crystalline solids, more stable, widely used industrial scales, easier/safer prepare. Therefore, recent years have witnessed upsurge employing α-carbonyl alternative surrogate transition activation. Unlike contain inherent serve a partner well weak directing group. This review will summarize progress made both categories reactions.

Language: Английский

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Direct synthesis of benzoxazinones via Cp*Co(III)-catalyzed C–H activation and annulation of sulfoxonium ylides with dioxazolones

Chinese Chemical Letters, Journal Year: 2020, Volume and Issue: 32(3), P. 1263 - 1266

Published: Sept. 16, 2020

Language: Английский

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Ruthenium-catalyzed coupling of α-carbonyl phosphoniums with sulfoxonium ylides via C–H activation/Wittig reaction sequences

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(21), P. 2665 - 2668

Published: Jan. 1, 2021

A Ru(ii)-catalyzed coupling of various α-carbonyl phosphoniums with sulfoxonium ylides has been realized for the facile synthesis 1-naphthols in good to excellent yields.

Language: Английский

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Rh(III) Catalyzed Redox-Neutral C–H Activation/[5 + 2] Annulation of Aroyl Hydrazides and Sulfoxonium Ylides: Synthesis of Benzodiazepinones

Organic Letters, Journal Year: 2023, Volume and Issue: 25(46), P. 8361 - 8366

Published: Nov. 14, 2023

We herein report the Rh(III) catalyzed redox-neutral C–H activation/[5 + 2] annulation of aroyl hydrazides with sulfoxonium ylides as safe carbene precursors. The reaction shows excellent functional group tolerance, broad substrate scope, and scalability. demonstrated synthetic utility protocol via synthesis various diazepam drug analogues, late-stage functionalization probenecid drug, large scale synthesis. Finally, kinetic studies revealed activation rate-determining step.

Language: Английский

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