Mechanism of palladium-catalyzed diene cyclization/hydrosilylation: direct observation of intramolecular carbometalation.

Journal Article

The results of kinetic, deuterium-labeling, and low-temperature NMR studies have established a mechanism for the palladium-catalyzed cyclization/hydrosilylation of dimethyl diallylmalonate (1) with triethylsilane involving rapid, irreversible conversion of the palladium silyl complex [(phen)Pd(SiEt(3))(NCAr)](+) [BAr(4)](-) [Ar = 3,5-C(6)H(3)(CF(3))(2)] (4b) and 1 to the palladium 5-hexenyl chelate complex [(phen)Pd[eta(1),eta(2)-CH(CH(2)SiEt(3))CH(2)C(CO(2)Me)(2)CH(2)CH=CH(2)]](+) [BAr(4)](-) (5), followed by intramolecular carbometalation of 5 to form the palladium cyclopentylmethyl complex trans-[(phen)Pd[CH2CHCH2C(CO2Me)2CH2CHCH2SiEt3](NCAr)]+ [BAr4]- (6), and associative silylation of 6 to release 3 and regenerate 4b.

Full Text

Duke Authors

Cited Authors

  • Perch, NS; Widenhoefer, RA

Published Date

  • May 26, 2004

Published In

Volume / Issue

  • 126 / 20

Start / End Page

  • 6332 - 6346

PubMed ID

  • 15149231

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/ja049806f

Language

  • eng

Conference Location

  • United States