Recent advances in catalytic asymmetric alkenyl C(sp2)–H bond functionalizations

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review summarizes recent advances in asymmetric alkenyl C–H bond functionalization reactions, as well provides an outlook on future opportunities and challenges.

Язык: Английский

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Reflexive Chirality Transfer (RCT): Asymmetric 1,3-Dipolar Cycloaddition of α-Amino Acid Schiff Base with Nonchiral Copper Catalyst

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

Although optically pure α-amino acids are ubiquitous, their chirality is usually lost during the α-C-H deprotonation. Consequently, precious chiral catalysis has been necessary to synthesize active α-tetrasubstituted unnatural acid derivatives, even when starting with acids. However, here, we report a catalytic asymmetric 1,3-dipolar cycloaddition that preserves α-carbon of derivatives. This process directly converts readily available Schiff bases into pyrrolidine derivatives without external additives, despite temporary loss through formation planar 1,3-dipole intermediates. Mechanistic studies revealed base transiently transferred metal-centered in enolates and subsequently restored as carbon-centered products. conceptually novel "reflexive transfer (RCT)" strategy offers simple cost-effective approach addressing current limitations pool synthesis.

Язык: Английский

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Diastereodivergent Parallel Kinetic Resolution of Racemic 2-Substituted Pyrrolidines via Iridium-Catalyzed C(sp³)–H Borylation

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 18701 - 18707

Опубликована: Дек. 8, 2024

Chiral 2,5-disubstituted pyrrolidines are ubiquitous subunits in natural products, bioactive compounds, pharmaceuticals, and chiral catalysts. However, their asymmetric synthesis still presents a formidable challenge. We herein report rare example of diastereodivergent parallel kinetic resolution racemic 2-substituted via C(sp3)–H borylation. A vast array enantioenriched cis- trans-2,5-disubstituted were obtained with high enantioselectivities. The synthetic utility was demonstrated by downstream transformations, including the optically active pyrrolidine 197B cis-pyrrolidine 225H.

Язык: Английский

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A bifunctional coumarin-based CD probe for chiral analysis of amino acids in aqueous solution

Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy, Год журнала: 2024, Номер unknown, С. 125654 - 125654

Опубликована: Дек. 1, 2024

Язык: Английский

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