Enantioselective Synthesis of Axially Chiral Alkylidenecycloalkanes via Copper-Catalyzed Functionalization of Acyl Allenols

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-01-24 DOI:10.1021/acscatal.4c06387

Baihui Gong, Qingbin Lu, Ruikang Sun, Zelin Li, Yihan Chen, Aijun Lin, Hequan Yao, Shang Gao

引用次数: 0

Abstract

Axially chiral alkylidenecycloalkanes are an important type of stereoisomer, resulting from the perpendicular arrangement of two pairs of substituents. Despite the considerable progress made in the catalytically enantioselective synthesis of atropisomers, the available methods for accessing axially chiral alkylidenecycloalkanes have been underutilized. In this study, we describe a copper-catalyzed enantioselective synthesis of axially chiral alkylidenecycloalkanes using acyl allenols. The axial chirality is established through a central to axial transfer via an enantioenriched allylcopper species. This reaction features mild conditions, >30:1 regioselectivities, and up to 98% ee. Control experiments reveal that the bulky size of the leaving group has a significant influence on the enantioselectivity of the reaction. The alkene and vinylboronate groups of the products provide versatile platforms for further transformations to enrich the structural diversity of products.

Abstract Image

查看原文本刊更多论文

求助全文

约1分钟内获得全文求助全文

来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.