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光催化乙烯基硅烷与路易斯碱的E→Z反热力学异构化反应

Photocatalytic E→Z Contra-Thermodynamic Isomerization of Vinyl Silanes with Lewis Base.

作者信息

Le Thi Minh Thi, Brégent Thibaud, Jubault Philippe, Poisson Thomas

机构信息

Normandie Univ., INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), 76000, Rouen, France.

Institut Universitaire de France, 1 rue Descartes, 75231, Paris, France.

出版信息

Chemistry. 2022 Sep 16;28(52):e202201514. doi: 10.1002/chem.202201514. Epub 2022 Jul 22.

Abstract

Herein, we disclosed the contra-thermodynamic E→Z isomerization of alkenyl silanes, according to the in situ formation of a chromophoric species, in the presence of rac-BINAP as the catalyst. The reaction carried out in DMSO or CH CN under irradiation at 405 nm allowed the interconversion of the E-isomers into the Z-congeners in good to excellent yields and outstanding Z/E selectivities, on 18 examples. Finally, the mechanism of this E→Z isomerization was studied to get insight into the reaction mechanism.

摘要

在此,我们揭示了在rac-BINAP作为催化剂存在的情况下,根据发色物种的原位形成,烯基硅烷的反热力学E→Z异构化反应。在二甲基亚砜(DMSO)或乙腈(CH₃CN)中于405 nm光照下进行的该反应,使18个实例中的E异构体以良好至优异的产率和出色的Z/E选择性转化为Z异构体。最后,对这种E→Z异构化的机理进行了研究,以深入了解反应机理。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/60fa/9541780/b876097c0648/CHEM-28-0-g005.jpg

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