Photocatalytic Giese‐Type Reaction with Alkylsilicates Bearing C,O‐Bidentate Ligands
Photocatalytic Giese‐Type Reaction with Alkylsilicates Bearing C,O‐Bidentate Ligands
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带有 C,O-二齿配体的烷基硅酸盐的光催化吉斯型反应
DOI：
10.1002/chem.202005300
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Naokazu Kano
中科院分区：
文献类型：
--
作者：
Tatsuya Morofuji;Yu Matsui;Misa Ohno;Gun Ikarashi; Naokazu Kano
本文报道了一种以含C，O双齿配体的烷基硅酸盐作为稳定的烷基自由基前体的光催化Giese型反应。以有机金属为原料，一步制得烷基硅酸盐。该反应体系不仅可以生成伯、仲、叔烷基自由基，还可以生成难以捉摸的甲基自由基。生成的自由基被带有不同官能团的缺电子烯烃捕获，得到所需的烷基加合物。光化学反应后可回收硅副产物。通过理论计算研究了自由基的生成过程，这为含C，O -双齿配体的甲基硅酸盐容易生成甲基自由基提供了新的思路。
Herein, a photocatalytic Giese‐type reaction with alkylsilicates bearing C,O‐bidentate ligands as stable alkyl radical precursors has been reported. The alkylsilicates were prepared in one step from organometallic reagents. Not only primary, secondary, and tertiary alkyl radicals, but also elusive methyl radicals, could be generated by using the present reaction system. The generated radicals were trapped by electron‐deficient olefins bearing various functional groups to give the desired alkyl adducts. The silicon byproduct can be recovered after the photoreaction. The radical generation process was investigated by theoretical calculations, which provided an insight into the facile generation of methyl radicals from methylsilicate bearing C,O‐bidentate ligands.