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Rational design of a second generation catalyst for preparation of allylsilanes using the silyl-Heck reaction.

ABSTRACT: Using rational ligand design, we have developed of a second-generation ligand, bis(3,5-di-tert-butylphenyl)(tert-butyl)phosphine, for the preparation of allylsilanes using the palladium-catalyzed silyl-Heck reaction. This new ligand provides nearly complete suppression of starting material alkene isomerization that was observed with our first-generation catalyst, providing vastly improved yields of allylsilanes from simple alkene starting materials. The studies quantifying the electronic and steric properties of the new ligand are described. Finally, we report an X-ray crystal structure of a palladium complex resulting from the oxidative addition of Me3SiI using an analogous ligand that provides significant insight into the nature of the catalytic system.

SUBMITTER: McAtee JR

PROVIDER: S-EPMC4105080 | biostudies-literature | 2014 Jul

REPOSITORIES: biostudies-literature

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Rational design of a second generation catalyst for preparation of allylsilanes using the silyl-Heck reaction.

McAtee Jesse R JR Yap Glenn P A GP Watson Donald A DA

Journal of the American Chemical Society 20140708 28

Using rational ligand design, we have developed of a second-generation ligand, bis(3,5-di-tert-butylphenyl)(tert-butyl)phosphine, for the preparation of allylsilanes using the palladium-catalyzed silyl-Heck reaction. This new ligand provides nearly complete suppression of starting material alkene isomerization that was observed with our first-generation catalyst, providing vastly improved yields of allylsilanes from simple alkene starting materials. The studies quantifying the electronic and ste ...[more]

PMID: 25003502

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