Scope and Mechanism of the Pt-Catalyzed Enantioselective Diboration of Monosubstituted Alkenes

被引：114

作者：

Coombs, John R. ^{[1
]}

Haeffner, Fredrik ^{[1
]}

Kliman, Laura T. ^{[1
]}

Morken, James P. ^{[1
]}

机构：

[1] Boston Coll, Dept Chem, Merkert Chem Ctr, Chestnut Hill, MA 02467 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 30期

关键词：

GENERATED IN-SITU; BORONIC ESTERS; PLATINUM(0)-CATALYZED DIBORATION; PALLADIUM(0) COMPLEXES; OXIDATIVE ADDITION; TERMINAL ALKENES; ASYMMETRIC HYDROBORATION; MOLECULAR-STRUCTURES; PLATINUM COMPLEXES; HYDROGEN-PEROXIDE;

D O I：

10.1021/ja4041016

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The Pt-catalyzed enantioselective diboration of terminal alkenes can be accomplished in an enantioselective fashion in the presence of chiral phosphonite ligands. Optimal procedures and the substrate scope of this transformation are fully investigated. Reaction progress kinetic analysis and kinetic isotope effects suggest that the stereodefining step in the catalytic cycle is olefin migratory insertion into a Pt-B bond. Density functional theory analysis, combined with other experimental data, suggests that the insertion reaction positions platinum at the internal carbon of the substrate. A stereochemical model for this reaction is advanced that is in line both with these features and with the crystal structure of a Pt-ligand complex.

引用

页码：11222 / 11231

页数：10

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