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Publication 57  

  1. A General Nickel-Catalyzed Kumada Vinylation for the Preparation of 2-Substituted 1,3-Dienes
    Daniele Fiorito, Sarah Folliet, Yangbin Liu, Clément Mazet*
    ACS Catal. 2018, 8, 1392-1398

The identification of two nickel(II) precatalysts for the preparation of 2-substituted 1,3-dienes by a Kumada cross-coupling between vinyl magnesium bromide and vinyl phosphates is described. This is noteworthy as engaging already only one vinyl derivative in a transition metal-catalyzed cross-coupling reaction is reputedly challenging. Salient features of this method are its operational simplicity, the mild reaction conditions, the low catalyst loadings, the short reaction times, its scalability, and the use of stoichiometric quantities of each coupling partner. The tolerance of the two nickel catalysts to an important number of reactive functional groups and their compatibility with structurally complex molecular architectures has been extensively delineated. A Negishi variant of the reaction has been developed for even more sensitive organic functions such as ester or nitrile. Several other conjugated 1,3-dienes with various substitution patterns have been prepared by combining commercial alkenyl Grignard reagents and/or readily available alkenyl enol phosphates. Proper choice of the nickel catalyst and of the reaction temperature gave access to a variety of different olefin isomers with high levels of stereocontrol. In fine, this approach affords conjugated dienes that would not be accessible otherwise and therefore provides a valuable complement to existing methods.

open archive unige:101654

Editor’s version DOI: 10.1021/acscatal.7b04030 

AAM DOI: 10.26037/yareta:tch2gkdkhjhstk5iqeg2vsfcwm 

Dataset DOI: 10.26037/yareta:jk5xk366sndpnl4vil6iqdcide