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Organocuprate cross-coupling: The central role of the copper(III) intermediate and the importance of the Copper(I) precursor

被引：79
作者：
Bertz, Steven H.
Cope, Stephen
Dorton, Donna
Murphy, Michael
Ogle, Craig A.
机构：
[1] Complex Study Ctr, Mendham, NJ 07945 USA
[2] Univ N Carolina, Dept Chem, Charlotte, NC 28223 USA
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2007年 / 46卷 / 37期
关键词：
copper; cross-coupling; isotopic labeling; NMR spectroscopy; S ligands;
D O I：
10.1002/anie.200703035
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
(Chemical Equation Presented) CuIII in focus: The key intermediate in copper-mediated cross-coupling reactions has long been believed to be a copper-(III) intermediate". Investigation of reactions of a variety of methyl Gilman reagents Me2CuLi·LiX with Etl using rapid-injection NMR spectroscopy conditions reveals a number of formally Cu III tetra-coordinate square-planar intermediates (see scheme) with a surprising range of stabilities. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA."
引用
收藏
页码：7082 / 7085
页数：4
相关论文
共 41 条
[1]  
[Anonymous], 1995, ANGEW CHEM
[2]  
[Anonymous], MODERN ORGANOCOPPER
[3]   Copper in cross-coupling reactions - The post-Ullmann chemistry [J].
Beletskaya, IP ;
Cheprakov, AV .
COORDINATION CHEMISTRY REVIEWS, 2004, 248 (21-24) :2337-2364
[4]  
BERNERSPRICE SJ, 1985, INORG CHEM, V24, P3425
[5]   PREPARATION OF ETHEREAL LITHIUM DIMETHYLCUPRATES (ME(2)CULI)(2) AND ME(2)CULI.LII DISPLAYING NARROW-LINE WIDTH C-13 NMR RESONANCES [J].
BERTZ, SH ;
VELLEKOOP, AS ;
SMITH, RAJ ;
SNYDER, JP .
ORGANOMETALLICS, 1995, 14 (03) :1213-1220
[6]   NEW COPPER CHEMISTRY .20. LITHIUM CYANOCUPRATES, RCU(CN)LI - 1ST OBSERVATION OF 2-BOND C-13-C-13 NMR COUPLINGS IN ORGANOCUPRATES [J].
BERTZ, SH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (14) :5470-5471
[7]   It's on lithium! An answer to the recent communication which asked the question: 'If the cyano ligand is not on copper, then where is it?' [J].
Bertz, SH ;
Miao, GB ;
Eriksson, M .
CHEMICAL COMMUNICATIONS, 1996, (07) :815-816
[8]   ORGANOCUPRATE REACTIONS WITH CYCLOPROPANES - EVIDENCE FOR 3 TYPES OF MECHANISM [J].
BERTZ, SH ;
DABBAGH, G ;
COOK, JM ;
HONKAN, V .
JOURNAL OF ORGANIC CHEMISTRY, 1984, 49 (10) :1739-1743
[9]   Rapid injection NMR in mechanistic organocopper chemistry. Preparation of the elusive copper(III) intermediate [J].
Bertz, Steven H. ;
Cope, Stephen ;
Murphy, Michael ;
Ogle, Craig A. ;
Taylor, Brad J. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (23) :7208-+
[10]  
Canisius J, 2001, CHEM-EUR J, V7, P2671, DOI 10.1002/1521-3765(20010618)7:12<2671::AID-CHEM26710>3.0.CO
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