Breaking the regioselectivity rule for acrylate insertion in the Mizoroki-Heck reaction.

ABSTRACT: In modern methods for the preparation of small molecules and polymers, the insertion of substrate carbon-carbon double bonds into metal-carbon bonds is a fundamental step of paramount importance. This issue is illustrated by Mizoroki-Heck coupling as the most prominent example in organic synthesis and also by catalytic insertion polymerization. For unsymmetric substrates H(2)C = CHX the regioselectivity of insertion is decisive for the nature of the product formed. Electron-deficient olefins insert selectively in a 2,1-fashion for electronic reasons. A means for controlling this regioselectivity is lacking to date. In a combined experimental and theoretical study, we now report that, by destabilizing the transition state of 2,1-insertion via steric interactions, the regioselectivity of met

SUBMITTER: Wucher P 

PROVIDER: S-EPMC3107328 | biostudies-literature | 2011 May

REPOSITORIES: biostudies-literature