3252-91-3Relevant articles and documents
Electrochemical Nozaki-Hiyama-Kishi Coupling: Scope, Applications, and Mechanism
Baran, Phil S.,Blackmond, Donna G.,Gao, Yang,Hadt, Ryan G.,Hao, Wei,Hill, David E.,McNicholas, Brendon J.,Reisman, Sarah E.,Vantourout, Julien C.
supporting information, p. 9478 - 9488 (2021/07/19)
One of the most oft-employed methods for C-C bond formation involving the coupling of vinyl-halides with aldehydes catalyzed by Ni and Cr (Nozaki-Hiyama-Kishi, NHK) has been rendered more practical using an electroreductive manifold. Although early studies pointed to the feasibility of such a process, those precedents were never applied by others due to cumbersome setups and limited scope. Here we show that a carefully optimized electroreductive procedure can enable a more sustainable approach to NHK, even in an asymmetric fashion on highly complex medicinally relevant systems. The e-NHK can even enable non-canonical substrate classes, such as redox-active esters, to participate with low loadings of Cr when conventional chemical techniques fail. A combination of detailed kinetics, cyclic voltammetry, and in situ UV-vis spectroelectrochemistry of these processes illuminates the subtle features of this mechanistically intricate process.
Neighbouring-group influence on the ring opening of some 2-alkyl-1,1,2-tribromocyclopropanes under phase-transfer conditions
Sydnes, Leiv K.,Alnes, Karl F. S.,Erdogan, Natalia
, p. 1737 - 1749 (2007/10/03)
Several 2-alkyl-1,1,2-tribromocyclopropanes were treated with sodium hydroxide and ethanol under phase-transfer conditions. Ring opening gave mixtures of the corresponding acetylenic diethyl ketals and acetals. When the steric bulk of the alkyl substituent was increased acetal formation dominated, and in the case of 1,1,2-tribromo-2-(tert-butyl)cyclopropane, the acetal was formed as the only product. Springer-Verlag 2005.
Alkenyl bromides by brominative deoxygenation of ketones in one or two steps
Von Roman,Ruhdorfer,Knorr
, p. 985 - 992 (2007/10/02)
The conversion of ketones into alkenyl bromides is accomplished in one or two steps by 2,2,2-tribromo-2,2-dihydro-1,3,2-benzodioxaphosphole or by the dibromomethyl methyl ether prepared therefrom. Investigations of the scope and limitations provide some hints for the preparative planning and improvement.