期刊
CHEMICAL SCIENCE
卷 10, 期 17, 页码 4580-4587出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c9sc00711c
关键词
-
资金
- German Science Foundation (DFG) [GRK 1626, KO 1537/18-1]
- European Research Council (ERC) under the European Unions Horizon 2020 research and innovation programme [741623]
- China Scholarship Council (CSC) [201606280052]
- ERC [ERC CoG-614182]
Carbonyl-carbonyl olefination, known as McMurry reaction, represents a powerful strategy for the construction of olefins. However, catalytic variants that directly couple two carbonyl groups in a single reaction are less explored. Here, we report a photoredox-catalysis that uses B(2)pin(2) as terminal reductant and oxygen trap allowing for deoxygenative olefination of aromatic aldehydes under mild conditions. This strategy provides access to a diverse range of symmetrical and unsymmetrical alkenes with moderate to high yield (up to 83%) and functional-group tolerance. To follow the reaction pathway, a series of experiments were conducted including radical inhibition, deuterium labelling, fluorescence quenching and cyclic voltammetry. Furthermore, NMR studies and DFT calculations were combined to detect and analyze three active intermediates: a cyclic three-membered anionic species, an a-oxyboryl carbanion and a 1,1-benzyldiboronate ester. Based on these results, we propose a mechanism for the C] C bond generation involving a sequential radical borylation, bora-Brook rearrangement, B2pin2mediated deoxygenation and a boron-Wittig process.
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