Mechanism of rhodium-catalyzed carbene formation from diazo compounds

被引：51

作者：

Wong, Freeman M. ^{[1
]}

Wang, Jianbo

Hengge, Alvan C.

Wu, Weiming

机构：

[1] San Francisco State Univ, Dept Chem & Biochem, San Francisco, CA 94132 USA

[2] Utah State Univ, Dept Chem & Biochem, Logan, UT 84322 USA

[3] Peking Univ, Coll Chem, Key Lab Bioorgan Chem & Mol Engn, Minist Educ, Beijing 100871, Peoples R China

来源：

ORGANIC LETTERS | 2007年 / 9卷 / 09期

关键词：

D O I：

10.1021/ol070345n

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A large and normal nitrogen-15 kinetic isotope effect of 1.035 +/- 0.003 provides direct support for the proposed mechanism for the rhodium-catalyzed carbene formation from diazo compounds, which involves the fast formation of a metal-diazo complex followed by rate-limiting extrusion of N(2). The large magnitude of the KIE indicates extensive C-N bond fission in the transition state.

引用

页码：1663 / 1665

页数：3

共 32 条

[1] RHODIUM (II) CATALYZED-REACTIONS OF DIAZO-CARBONYL COMPOUNDS [J].

ADAMS, J ;

SPERO, DM .

TETRAHEDRON, 1991, 47 (10-11) :1765-1808

[2] KINETICS OF THE DIRHODIUM TETRAACETATE CATALYZED DECOMPOSITION OF ETHYL DIAZOACETATE IN 1,4-DIOXANE - IS NITROGEN INVOLVED IN THE TRANSITION-STATE [J].

ALONSO, ME ;

GARCIA, MD .

TETRAHEDRON, 1989, 45 (01) :69-76

[3]

ANICIAUX AJ, 1980, J ORG CHEM, V45, P695

[4]

BIGELEISEN J, 1958, ADV CHEM PHYS, V1, P15

[5] NITROGEN ISOTOPE EFFECTS IN DECOMPOSITION OF DIAZONIUM SALTS [J].

BROWN, LL ;

DRURY, JS .

JOURNAL OF CHEMICAL PHYSICS, 1965, 43 (05) :1688-&

[6] Recent progress in asymmetric intermolecular C-H activation by rhodium carbenoid intermediates [J].

Davies, HML ;

Antoulinakis, EG .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2001, 617 (01) :47-55

[7]

Doyle M. P., 1998, Modern Catalytic Methods for Organic Synthesis with Diazo Compounds: From Cyclopropanes to Ylides

[8] Recent advances in asymmetric catalytic metal carbene transformations [J].

Doyle, MP ;

Forbes, DC .

CHEMICAL REVIEWS, 1998, 98 (02) :911-935

[9] CATALYTIC METHODS FOR METAL CARBENE TRANSFORMATIONS [J].

DOYLE, MP .

CHEMICAL REVIEWS, 1986, 86 (05) :919-939

[10] ELECTRONIC AND STERIC CONTROL IN CARBON HYDROGEN INSERTION REACTIONS OF DIAZOACETOACETATES CATALYZED BY DIRHODIUM(II) CARBOXYLATES AND CARBOXAMIDES [J].

DOYLE, MP ;

WESTRUM, LJ ;

WOLTHUIS, WNE ;

SEE, MM ;

BOONE, WP ;

BAGHERI, V ;

PEARSON, MM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (03) :958-964

← 1 2 3 4 →