Mechanisms of Nucleophilic Organocopper(I) Reactions

被引：327

作者：

Yoshikai, Naohiko ^{[2
]}

Nakamura, Eiichi ^{[1
]}

机构：

[1] Univ Tokyo, Sch Sci, Dept Chem, Bunkyo Ku, Tokyo 1130033, Japan

[2] Nanyang Technol Univ, Sch Phys & Math Sci, Div Chem & Biol Chem, Singapore 637371, Singapore

来源：

CHEMICAL REVIEWS | 2012年 / 112卷 / 04期

关键词：

ORGANOCUPRATE CONJUGATE ADDITION; CROSS-COUPLING REACTION; HIGHER-ORDER CYANOCUPRATE; RAY CRYSTAL-STRUCTURE; CARBON BOND FORMATION; COPPER-CATALYZED TRIFLUOROMETHYLATION; ENANTIOSELECTIVE ALPHA-ARYLATION; 1ST STRUCTURAL-CHARACTERIZATION; DIALKYLCOPPER-LITHIUM REAGENTS; MEDIATED ALLYLIC SUBSTITUTION;

D O I：

10.1021/cr200241f

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A study was conducted to demonstrate mechanisms of nucleophilic organocopper(I) reactions. A comprehensive mechanistic picture of representative organocopper(I)-mediated C C bond-forming reactions was demonstrated. The structures of organocopper compounds, organocopper(I) ate complexes, and organocopper(III) complexes were described. The electronic structure of organocuprate(I) complexes and theirmolecular orbital interactions with electrophiles were discussed to gather information about the oxidative addition process of the organocuprate reactions. This demonstrated the way Lewis acidic countercations affected the organocuprate reaction and how organocopper(III) intermediates produced the C C coupling products. Organocopper reagents were also compared with organosilver and -gold analogues.

引用

页码：2339 / 2372

页数：34

共 529 条

[1] Enantioselective copper-catalyzed conjugate addition and allylic substitution reactions [J].

Alexakis, A. ;

Backvall, J. E. ;

Krause, N. ;

Pamies, O. ;

Dieguez, M. .

CHEMICAL REVIEWS, 2008, 108 (08) :2796-2823

[2] Dramatic improvement of the enantiomeric excess in the asymmetric conjugate addition reaction using new experimental conditions [J].

Alexakis, A ;

Benhaim, C ;

Rosse, S ;

Humam, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (19) :5262-5263

[3] MECHANISTIC ASPECTS ON THE FORMATION OF CHIRAL ALLENES FROM PROPARGYLIC ETHERS AND ORGANOCOPPER REAGENTS [J].

ALEXAKIS, A ;

MAREK, I ;

MANGENEY, P ;

NORMANT, JF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (22) :8042-8047

[4]

ALEXAKIS A, 1984, ISRAEL J CHEM, V24, P113

[5] BORON FLUORIDE PROMOTED OPENING OF EPOXIDES BY ORGANOCOPPER AND CUPRATE REAGENTS [J].

ALEXAKIS, A ;

JACHIET, D ;

NORMANT, JF .

TETRAHEDRON, 1986, 42 (20) :5607-5619

[6] ORGANOCOPPER CONJUGATE ADDITION-REACTION IN THE PRESENCE OF TRIMETHYLCHLOROSILANE [J].

ALEXAKIS, A ;

BERLAN, J ;

BESACE, Y .

TETRAHEDRON LETTERS, 1986, 27 (09) :1047-1050

[7]

ALEXAKIS A, 1976, TETRAHEDRON LETT, P3461

[8]

ALEXAKIS A, 1977, B SOC CHIM FR II-CH, P693

[9] Synergistic dimetallic effects in propargylic substitution reaction catalyzed by thiolate-bridged diruthenium complex [J].

Ammal, SC ;

Yoshikai, N ;

Inada, Y ;

Nishibayashi, Y ;

Nakamura, E .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (26) :9428-9438

[10] STEREOSELECTIVE SYNTHESIS OF OLEFINS . REACTION OF DIALKYLCOPPER-LITHIUM REAGENTS WITH ALLYLIC ACETATES [J].

ANDERSON, RJ ;

HENRICK, CA ;

SIDDALL, JB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1970, 92 (03) :735-&

← 1 2 3 4 5 6 7 8 9 10 →