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

共 123 条

[11] Reaction progress kinetic analysis: A powerful methodology for mechanistic studies of complex catalytic reactions [J].

Blackmond, DG .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (28) :4302-4320

[12] Transition-Metal-Free Diboration Reaction by Activation of Diboron Compounds with Simple Lewis Bases [J].

Bonet, Amadeu ;

Pubill-Ulldemolins, Cristina ;

Bo, Caries ;

Gulyas, Henrik ;

Fernandez, Elena .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (31) :7158-7161

[13] Conversion of trans-bromoboryl platinum complexes into their cis-analogues upon treatment with chelating bisphosphines [J].

Braunschweig, Holger ;

Leech, Ralph ;

Rais, Daniela ;

Radacki, Krzysztof ;

Uttinger, Katharina .

ORGANOMETALLICS, 2008, 27 (03) :418-422

[14] FACILE REACTION OF ALKYLDICHLOROBORANES AND ARYLDICHLOROBORANES WITH ORGANIC AZIDES - GENERAL STEREOSPECIFIC SYNTHESIS OF SECONDARY-AMINES [J].

BROWN, HC ;

MIDLAND, MM ;

LEVY, AB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (07) :2394-2396

[15] ORGANOBORANES .45. AN EXPLORATION OF THE EFFECTIVENESS OF REPRESENTATIVE HOMOLOGATING AGENTS WITH VARIOUS ORGANOBORANE DERIVATIVES - R3B, R2BOR', AND RB(OR')2 [J].

BROWN, HC ;

SINGH, SM .

ORGANOMETALLICS, 1986, 5 (05) :998-1001

[16] DEVELOPMENT OF A SIMPLE GENERAL PROCEDURE FOR SYNTHESIS OF PURE ENANTIOMERS VIA CHIRAL ORGANOBORANES [J].

BROWN, HC ;

SINGARAM, B .

ACCOUNTS OF CHEMICAL RESEARCH, 1988, 21 (08) :287-293

[17] ORGANOBORANES .44. A MORE CONVENIENT, PRACTICAL ROUTE TO ACHIEVE THE HOMOLOGATION OF BORONIC ESTERS [J].

BROWN, HC ;

SINGH, SM .

ORGANOMETALLICS, 1986, 5 (05) :994-997

[18] ORGANOBORANES .46. NEW PROCEDURES FOR THE HOMOLOGATION OF BORONIC ESTERS - A CRITICAL-EXAMINATION OF THE AVAILABLE PROCEDURES TO ACHIEVE CONVENIENT HOMOLOGATION OF BORONIC ESTERS [J].

BROWN, HC ;

SINGH, SM ;

RANGAISHENVI, MV .

JOURNAL OF ORGANIC CHEMISTRY, 1986, 51 (16) :3150-3155

[19] ORGANOBORANES .32. HOMOLOGATION OF ALKYLBORONIC ESTERS WITH METHOXY(PHENYLTHIO)METHYLLITHIUM - REGIOCONTROLLED AND STEREOCONTROLLED ALDEHYDE SYNTHESIS FROM OLEFINS VIA HYDROBORATION [J].

BROWN, HC ;

IMAI, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (20) :6285-6289

[20] ORGANOBORANES FOR SYNTHESIS .2. OXIDATION OF ORGANOBORANES WITH ALKALINE HYDROGEN-PEROXIDE AS A CONVENIENT ROUTE FOR THE CIS-HYDRATION OF ALKENES VIA HYDROBORATION [J].

BROWN, HC ;

SNYDER, C ;

RAO, BCS ;

ZWEIFEL, G .

TETRAHEDRON, 1986, 42 (20) :5505-5510

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