Issue 2, 2019

Anti-Markovnikov terminal and gem-olefin hydrosilylation using a κ4-diimine nickel catalyst: selectivity for alkene hydrosilylation over ether C–O bond cleavage

Abstract

The phosphine-substituted α-diimine Ni precursor, (Ph2PPrDI)Ni, has been found to catalyze alkene hydrosilylation in the presence of Ph2SiH2 with turnover frequencies of up to 124 h−1 at 25 °C (990 h−1 at 60 °C). Moreover, the selective hydrosilylation of allylic and vinylic ethers has been demonstrated, even though (Ph2PPrDI)Ni is known to catalyze allyl ester C–O bond hydrosilylation. At 70 °C, this catalyst has been found to mediate the hydrosilylation of ten different gem-olefins, with turnover numbers of up to 740 under neat conditions. Prior and current mechanistic observations suggest that alkene hydrosilylation takes place though a Chalk–Harrod mechanism following phosphine donor dissociation.

Graphical abstract: Anti-Markovnikov terminal and gem-olefin hydrosilylation using a κ4-diimine nickel catalyst: selectivity for alkene hydrosilylation over ether C–O bond cleavage

Supplementary files

Article information

Article type
Paper
Submitted
21 nov 2018
Accepted
22 nov 2018
First published
23 nov 2018

Dalton Trans., 2019,48, 461-467

Author version available

Anti-Markovnikov terminal and gem-olefin hydrosilylation using a κ4-diimine nickel catalyst: selectivity for alkene hydrosilylation over ether C–O bond cleavage

C. L. Rock and R. J. Trovitch, Dalton Trans., 2019, 48, 461 DOI: 10.1039/C8DT04608E

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