Catalytic enantioselective reductive Eschenmoser-Claisen rearrangements

• 成果类型: Article
• 署名作者: Zhang, Guoting; Wodrich, Matthew D.; Cramer, Nicolai
• 署名单位: Swiss Federal Institutes of Technology Domain; Ecole Polytechnique Federale de Lausanne; Swiss Federal Institutes of Technology Domain; Ecole Polytechnique Federale de Lausanne
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-14056
• DOI: 10.1126/science.adl3369
• 发表日期: 2024-01-26
• 页码: 395-401
• 关键词: construction; ACID; desymmetrization; hydroboration; hydrolysis; mild

摘要

An important challenge in enantioselective catalysis is developing strategies for the precise synthesis of neighboring congested all-carbon quaternary stereocenters. The well-defined transition states of [3,3]-sigmatropic rearrangements and their underlying stereospecificity render them powerful tools for the synthesis of such arrays. However, this type of pericyclic reaction remains notoriously difficult to catalyze, especially in an enantioselective fashion. Herein, we describe an enantioselective reductive Eschenmoser-Claisen rearrangement catalyzed by chiral 1,3,2-diazaphospholene-hydrides. This developed transformation enables full control of the two newly formed acyclic stereogenic centers, leading to amides with vicinal all-carbon quaternary-tertiary or quaternary-quaternary carbon atoms.