Formation of Quaternary Chiral Centers by N-Heterocyclic Carbene-Cu-Catalyzed Asymmetric Conjugate Addition Reactions with Grignard Reagents on Trisubstituted Cyclic Enones

被引：93

作者：

Kehrli, Stefan ^{[1
]}

Martin, David ^{[2
]}

Rix, Diane ^{[3
]}

Mauduit, Marc ^{[3
]}

Alexakis, Alexandre ^{[1
]}

机构：

[1] Univ Geneva, Dept Chim Organ, CH-1211 Geneva 4, Switzerland

[2] UPCAM iSm2 Serv A62, F-3397 Marseille 20, France

[3] Ecole Natl Super Chim Rennes, F-35700 Rennes, France

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2010年 / 16卷 / 32期

基金：

新加坡国家研究基金会;

关键词：

asymmetry; conjugate addition; copper; Grignard reaction; N-heterocyclic carbenes; RING-CLOSING METATHESIS; ARYL ALUMINUM REAGENTS; STEREOGENIC CENTERS; ALLYLIC SUBSTITUTION; ENANTIOSELECTIVE SYNTHESIS; DIALKYLZINC REAGENTS; NHC LIGANDS; PHOSPHORAMIDITE LIGAND; UNSATURATED ESTERS; MELDRUMS ACIDS;

D O I：

10.1002/chem.201000471

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The copper-catalyzed conjugate addition of Grignard reagents to 3-substituted cyclic enones allows the formation of all-carbon chiral quaternary centers We demonstrate in this article that N-heterocyclic carbencs act as efficient chiral ligands for this transformation High enantioselectivities (up to 96% ee) could be obtained for a variety of substrates

引用

页码：9890 / 9904

页数：15

共 77 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] The copper-catalyzed asymmetric allylic substitution [J].

Alexakis, A ;

Malan, C ;

Lea, L ;

Tissot-Croset, K ;

Polet, D ;

Falciola, C .

CHIMIA, 2006, 60 (03) :124-130

[3] Asymmetric synthesis with N-heterocyclic carbenes.: Application to the copper-catalyzed conjugate addition [J].

Alexakis, A ;

Winn, CL ;

Guillen, F ;

Pytkowicz, J ;

Roland, S ;

Mangeney, P .

ADVANCED SYNTHESIS & CATALYSIS, 2003, 345 (03) :345-348

[4]

Alexakis A, 2002, EUR J ORG CHEM, V2002, P3221

[5]

[Anonymous], ANGEW CHEM

[6]

Bernardinelli, 2007, ANGEW CHEM, V119, P7606

[7] Iodine-catalyzed synthesis of β-keto enol ethers [J].

Bhosale, RS ;

Bhosale, SV ;

Wang, TY ;

Zubaidha, PK .

TETRAHEDRON LETTERS, 2004, 45 (39) :7187-7188

[8] Stable carbenes [J].

Bourissou, D ;

Guerret, O ;

Gabbaï, FP ;

Bertrand, G .

CHEMICAL REVIEWS, 2000, 100 (01) :39-91

[9]

Brown M. K., 2007, Angew. Chem, V119, P1115

[10] Enantioselective total synthesis of clavirolide C. applications of Cu-catalyzed asymmetric conjugate additions and Ru-catalyzed ring-closing metathesis [J].

Brown, M. Kevin ;

Hoveyda, Amir H. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (39) :12904-+

← 1 2 3 4 5 6 7 8 →