An orthogonal bimetallicrelay catalytic strategy capable of enantioselectively imbedding a boryl functionality at a remote, less-activated site of aryl alkenes is disclosed. This approach was applicable to unactivated terminal and internal alkenes, as well as a mixture of olefin isomers, thus leading to the corresponding chiral products with a boryl-substituted stereogenic center β to a functional
of two different internal alkene isomers. The chromium catalyst, in the presence of HBpin/LiOtBu, enables the isomerization of alkenes over multiple carbon atoms to give the most thermodynamically stable isomers. The same catalyst allows for the selective isomerization of terminal alkenes over one carbon atom without an additive, exhibiting efficient and controllable alkene transposition selectivity
我们报告了一种单一的添加剂响应型铬催化系统,用于选择性生产两种不同的内部烯烃异构体中的任何一种。在 HBpin/LiO t Bu 存在下,铬催化剂能够使烯烃在多个碳原子上异构化,得到热力学最稳定的异构体。同一催化剂无需添加剂即可实现末端烯烃在一个碳原子上的选择性异构化,表现出高效且可控的烯烃转位选择性。
Dual role of allylsamarium bromide as a Grignard reagent and a single electron transfer reagent in the one-pot synthesis of terminal olefins
作者:Ying Li、Yuan-Yuan Hu、Song-Lin Zhang
DOI:10.1039/c3cc45611k
日期:——
The utility of allylsamarium bromide, both as a nucleophilic reagent and a single-electron transfer reagent, in the reaction of carbonyl compounds with allylsamarium bromide in the presence of diethyl phosphate is reported in this communication. From a synthetic point of view, a simple one-pot method for the preparation of terminal olefins is developed.
Radical Addition-Triggered Remote Migratory Isomerization of Unactivated Alkenes to Difluoromethylene-Containing Alkenes Enabled by Bimetallic Catalysis
A fascinating alkeneremote migratory isomerization engendered by carbon radical addition to C═C bond in alkenes via bimetalliccatalysis has been disclosed. A diverse array of alkenes bearing distantly incorporated the difluoromethylene (RCF2R′) functionality have been expediently obtained. The retainment of C═C bonds in products could serve as an useful synthetic platform furnishing otherwise difficult