期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 47, 页码 21176-21182出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202009893
关键词
homogeneous catalysis; cobalt; DFT calculations; hydroboration; selectivity
资金
- FCI
- Alexander Von Humboldt Foundation
- Projekt DEAL
Selectivity between 1,2 and 1,4 addition of a nucleophile to an alpha,beta-unsaturated carbonyl compound has classically been modified by the addition of stoichiometric additives to the substrate or reagent to increase their hard or soft character. Here, we demonstrate a conceptually distinct approach that instead relies on controlling the coordination sphere of a catalyst with visible light. In this way, we bias the reaction down two divergent pathways, giving contrasting products in the catalytic hydroboration of alpha,beta-unsaturated ketones. This includes direct access to previously elusive cyclic enolborates, via 1,4-selective hydroboration, providing a straightforward and stereoselective route to rare syn-aldol products in one-pot. DFT calculations and mechanistic experiments confirm two different mechanisms are operative, underpinning this unusual photocontrolled selectivity switch.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据