Rhodium-catalyzed enantioselective C–H alkynylation of sulfoxides in diverse patterns: desymmetrization, kinetic resolution, and parallel kinetic resolution

Kong, Lingheng; Zou, Yun; Li, Xiao Xi; Zhang, Xuepeng; Li, Xingwei

doi:10.1039/d2sc05310a

Cited by 7 publications

(2 citation statements)

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“…The Ru-catalyzed addition of phenyl boronic acid to an arylaldehyde provided a secondary alcohol 113 in 83% ee (Scheme g). Furthermore, the chiral carboxamide 109 was applied as a supplementary chiral source (20 mol %) in Rh(III)-catalyzed C–H alkynylation–desymmetrization of diphenyl sulfoxide (Scheme h), affording the desired alkyne 114 in excellent enantioselectivity. Control experiments verified that a common additive such as LiOAc or an achiral amide afforded only poor outcomes.…”

Section: Resultsmentioning

confidence: 99%

Intermolecular Buchwald–Hartwig Reactions for Enantioselective Synthesis of Diverse Atropisomers: Rerouting the C–N Forming Mechanism to Substrate Oxygen-Assisted Reductive Elimination

Wang,

Jiang,

et al. 2024

J. Am. Chem. Soc.

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Axially chiral biaryls featuring a C−N axis are important functional molecules in diverse fields. The asymmetric Buchwald−Hartwig reaction represents a powerful strategy for these targets. Previous studies, however, have been predominantly restricted to intramolecular atroposelective coupling, likely due to the steric and entropic effects in the reductive elimination of Pd(II) species with sterically congested aryl and nitrogen groups. We now report two intermolecular Buchwald−Hartwig coupling systems of bulky NH lactams and halohydrocarbons enabled by rerouting the mechanism of C−N reductive elimination to one that accommodates sterically challenging substrates. Both atroposelective coupling systems exhibited functional group tolerance, excellent enantioselectivity, and high Z selectivity (if applicable), affording C− N atropisomeric biaryl and olefins through de novo construction of a C−N chiral axis. Experimental and computational studies were performed to elucidate the mechanism, and the switch of the reaction pathways is traced to the steric effect (ortho substituent) of the aryl halide substrate. A bulky 2,6-disubstituted aryl halide reorients the proximal lactamide ligand to its unusual O-ligation mode. With the amide oxygen participation, this intermediate undergoes C−N reductive elimination with an accessible barrier through a five-membered ring transition state, a pathway as well as a chiral induction mode that has been much underexplored in asymmetric catalysis.

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Section: Resultsmentioning

confidence: 99%

Intermolecular Buchwald–Hartwig Reactions for Enantioselective Synthesis of Diverse Atropisomers: Rerouting the C–N Forming Mechanism to Substrate Oxygen-Assisted Reductive Elimination

Wang,

Jiang,

et al. 2024

J. Am. Chem. Soc.

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“…207 Li and co-workers recently revealed a sulfoxide-directed, Rh(III)-catalyzed asymmetric C−H alkynylation. 208 Utilizing the combination of Rh-2q and A-9 as cocatalyst, the enantioselective synthesis of various S-chiral sulfoxides 289 was achieved in good yields and enantioselectivity (up to 97% yield and 98% ee, Scheme 47). Impressively, under the same conditions, both kinetic and parallel kinetic resolution could be realized in good results.…”

Section: Rh(iii)-catalyzed Asymmetric C−h Functionalization Reactions...mentioning

confidence: 99%

Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Liu,

Yin,

Zhao

et al. 2023

Chem. Rev.

105

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This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during the last two decades. Parallel to the rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity in asymmetric C–H functionalization reactions. In recent years, Rh-catalyzed asymmetric C–H functionalization reactions have been significantly developed in many respects, including catalyst design, reaction development, mechanistic investigation, and application in the synthesis of complex functional molecules. This review presents an explicit outline of catalysts and ligands, mechanism, the scope of coupling reagents, and applications.

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Rh‐catalyzed Asymmetric C(sp³)−H Arylation of 8‐Benzylquinolines with Arylboronic Acids

Zhang,

Gou,

Wang

et al. 2023

Adv Synth Catal

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Rh‐catalyzed asymmetric C(sp3)‐H arylation of 8‐benzylquinolines with arylboronic acids was developed. In the presence of 5 mol% BINOL‐derived chiral cyclopentadienyl rhodium complex, asymmetric benzylic C(sp3)‐H bond arylation reaction proceeded smoothly to afford a series of enantioenriched triarylmethanes in moderate to good yields with good to excellent enantioselective control (24‐89% yields, 63‐93% ee). The method displays a broad substrate scope and good functional group tolerance under mild conditions.

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Rhodium-catalyzed enantioselective C–H alkynylation of sulfoxides in diverse patterns: desymmetrization, kinetic resolution, and parallel kinetic resolution

Abstract: Rhodium-catalyzed enantioselective C-H alkynylation of achiral and racemic sulfoxides is disclosed with alkynyl bromide as the alkynylating reagent. A wide range of chiral sulfoxides have been constructed in good yield...

Cited by 7 publications

References 93 publications

Intermolecular Buchwald–Hartwig Reactions for Enantioselective Synthesis of Diverse Atropisomers: Rerouting the C–N Forming Mechanism to Substrate Oxygen-Assisted Reductive Elimination

Intermolecular Buchwald–Hartwig Reactions for Enantioselective Synthesis of Diverse Atropisomers: Rerouting the C–N Forming Mechanism to Substrate Oxygen-Assisted Reductive Elimination

Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Rh‐catalyzed Asymmetric C(sp³)−H Arylation of 8‐Benzylquinolines with Arylboronic Acids

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Rhodium-catalyzed enantioselective C–H alkynylation of sulfoxides in diverse patterns: desymmetrization, kinetic resolution, and parallel kinetic resolution

Abstract: Rhodium-catalyzed enantioselective C-H alkynylation of achiral and racemic sulfoxides is disclosed with alkynyl bromide as the alkynylating reagent. A wide range of chiral sulfoxides have been constructed in good yield...

Cited by 7 publications

References 93 publications

Intermolecular Buchwald–Hartwig Reactions for Enantioselective Synthesis of Diverse Atropisomers: Rerouting the C–N Forming Mechanism to Substrate Oxygen-Assisted Reductive Elimination

Intermolecular Buchwald–Hartwig Reactions for Enantioselective Synthesis of Diverse Atropisomers: Rerouting the C–N Forming Mechanism to Substrate Oxygen-Assisted Reductive Elimination

Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Rh‐catalyzed Asymmetric C(sp3)−H Arylation of 8‐Benzylquinolines with Arylboronic Acids

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Rh‐catalyzed Asymmetric C(sp³)−H Arylation of 8‐Benzylquinolines with Arylboronic Acids