在超硅烷基路易斯酸促进的木山羟醛反应中的化学选择性硅烷基转移

Chemoselective silyl transfer in the Mukaiyama aldol reaction promoted by super silyl Lewis acid.

作者信息

Sai Masahiro, Akakura Matsujiro, Yamamoto Hisashi

机构信息

Molecular Catalyst Research Center, Chubu University, 1200 Matsumoto-cho, Kasugai, Aichi 487-8501, Japan.

出版信息

Chem Commun (Camb). 2014 Dec 14;50(96):15206-8. doi: 10.1039/c4cc05807k.

DOI:10.1039/c4cc05807k

PMID:25338752

Abstract

In the silyl Lewis acid-promoted Mukaiyama aldol reaction, the steric and electronic properties of the silyl group on the silyl Lewis acid influence the reaction mechanism and product distribution. When super silyl triflates such as (TMS)3SiOTf and (TES)3SiOTf are used as Lewis acids, the silyl group of the silyl enol ether chemoselectively transfers to the product. The mechanistic details have been investigated using density functional theory (DFT) calculations.

摘要

在硅基路易斯酸促进的 Mukaiyama 羟醛缩合反应中，硅基路易斯酸上硅基的空间和电子性质会影响反应机理和产物分布。当使用超硅基三氟甲磺酸盐，如（三甲基硅基）三甲基硅基三氟甲磺酸盐和（三乙基硅基）三乙基硅基三氟甲磺酸盐作为路易斯酸时，硅基烯醇醚的硅基会化学选择性地转移到产物上。已使用密度泛函理论（DFT）计算研究了其详细机理。