Organocatalytic asymmetric synthesis of Si-stereogenic silacycles

作者：Jung Tae Han, Nobuya Tsuji, Hui Zhou, Markus Leutzsch, Benjamin List · 发表于：Nature Communications · 年份：2024 · DOI：10.1038/s41467-024-49988-2 · 被引用次数：20 · 研究领域：Organoboron and organosilicon chemistry、Synthetic Organic Chemistry Methods、Cyclopropane Reaction Mechanisms

A strong and confined Brønsted acid catalyzed enantioselective cyclization of bis(methallyl)silanes provides enantioenriched Si-stereogenic silacycles. High enantioselectivities of up to 96.5:3.5 er were obtained for a range of bis(methallyl)silanes. NMR and ESI-MS studies reveal that the formation of a covalent adduct irreversibly inhibits turnover. Remarkably, we found that acetic acid as an additive promotes the collapse of this adduct, enabling full turnover. Experimental investigation and density functional theory (DFT) calculations were conducted to elucidate the origin of this phenomenon and the observed enantioselectivity.