Le Thi Minh Thi, Brégent Thibaud, Jubault Philippe, Poisson Thomas
Normandie Univ., INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), 76000, Rouen, France.
Institut Universitaire de France, 1 rue Descartes, 75231, Paris, France.
Chemistry. 2022 Sep 16;28(52):e202201514. doi: 10.1002/chem.202201514. Epub 2022 Jul 22.
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.
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。