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

被引：35

作者：

Perch, NS ^{[1
]}

Widenhoefer, RA ^{[1
]}

机构：

[1] Duke Univ, Paul M Gross Chem Lab, Durham, NC 27708 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 20期

关键词：

D O I：

10.1021/ja049806f

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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(SiEt3)(NCAr)](+) [BAr4](-) [Ar = 3,5-C6H3(CF3)(2)] (4b) and 1 to the palladium 5-hexenyl chelate complex {(phen)Pd[eta(1), eta(2)-CH(CH2SiEt3)CH2C(CO2Me)(2)CH2CH=CH2]}(+) [BAr4](-) (5), followed by intramolecular carbometalation of 5 to form the palladium cyclopentylmethyl complex trans-{(phen)Pd[CH2CHCH2C(CO2Me)(2)CH2CHCH2SiEt3]-(NCAr)}(+) [BAr4](-) (6), and associative silylation of 6 to release 3 and regenerate 4b.

引用

页码：6332 / 6346

页数：15

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