可见光介导的硅基烯醇醚与芳基重氮乙酸酯的形式烷基化和[4+1]环加成策略

Visible light-mediated formal alkylation and [4+1]-cycloaddition strategies of silyl enol ethers with aryldiazoacetates.

作者信息

Cariello Guilherme, Gallo Rafael D C, Deflon Victor M, Cormanich Rodrigo A, Jurberg Igor D

机构信息

Universidade Estadual de Campinas, Instituto de Química, CEP 13083-862, Campinas, SP, Brazil.

Universidade de São Paulo, Instituto de Química de São Carlos, CEP 13566-590, São Carlos, SP, Brazil.

出版信息

Chem Commun (Camb). 2025 Jan 28;61(10):2044-2047. doi: 10.1039/d4cc05451b.

DOI:10.1039/d4cc05451b

PMID:39670804

Abstract

A reaction sequence of visible light-mediated cyclopropanation/acid-promoted ring-opening is described for the formal alkylation of silyl enol ethers with aryldiazoacetates. Under the same conditions, the Danishefsky's diene can react with aryldiazoacetates to afford [4+1]-cycloaddition adducts. Key mechanistic aspects are proposed based on experimental evidence and DFT calculations.

摘要

描述了一种用于硅烯醇醚与芳基重氮乙酸酯进行形式烷基化的可见光介导的环丙烷化/酸促进的开环反应序列。在相同条件下，丹尼谢夫斯基双烯可与芳基重氮乙酸酯反应，得到[4+1]环加成加合物。基于实验证据和密度泛函理论计算提出了关键的机理方面。