Catalytic enantioselective alkylations of tetrasubstituted olefins. Synthesis of all-carbon quaternary stereogenic centers through Cu-catalyzed asymmetric conjugate additions of alkylzinc reagents to enones

被引：116

作者：

Hird, AW ^{[1
]}

Hoveyda, AH ^{[1
]}

机构：

[1] Boston Coll, Merkert Chem Ctr, Dept Chem, Chestnut Hill, MA 02467 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2005年 / 127卷 / 43期

关键词：

D O I：

10.1021/ja0553811

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A method for Cu-catalyzed asymmetric conjugate addition (ACA) of dialkylzinc reagents to tetrasubstituted five- and six-membered cyclic enones that afford quaternary all-carbon stereogenic centers in up to 95% ee is reported. Catalytic ACAs are practical and efficient. Reactions proceed to >98% conversion in undistilled commercial grade toluene in the presence of 2 mol % of an air-stable Cu salt (CuCN) and a readily available chiral ligand. Enantioselective ACA reactions deliver products that can be readily functionalized to afford a variety of synthetically versatile compounds in high optical purity. Copyright © 2005 American Chemical Society.

引用

页码：14988 / 14989

页数：2

共 41 条

[1] Catalytic enantioselective alkylations of tetrasubstituted olefins. Synthesis of all-carbon quaternary stereogenic centers through Cu-catalyzed asymmetric conjugate additions of alkylzinc reagents to enones
Hird, Alexander W.
Hoveyda, Amir H.
Journal of the American Chemical Society, 2005, 127 (43): : 14988 - 14989
[2] Enantioselective synthesis of nitroalkanes bearing all-carbon quaternary stereogenic centers through Cu-catalyzed asymmetric conjugate additions
Wu, J
Mampreian, DM
Hoveyda, AH
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (13) : 4584 - 4585
[3] Catalytic enantioselective synthesis of quaternary all-carbon stereogenic centers.: Preparation of α,α'-disubstituted β,γ-unsaturated esters through Cu-catalyzed asymmetric allylic alkylations
Murphy, KE
Hoveyda, AH
ORGANIC LETTERS, 2005, 7 (07) : 1255 - 1258
[4] Cu-catalyzed asymmetric conjugate additions of alkylzinc reagents to acyclic aliphatic enones
Mizutani, H
Degrado, SJ
Hoveyda, AH
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (05) : 779 - 781
[5] Cu-catalyzed asymmetric conjugate additions of alkylzinc reagents to acyclic aliphatic enones
Hoveyda, A.H., 1600, American Chemical Society (124):
[6] All-carbon quaternary stereogenic centers by enantioselective Cu-catalyzed conjugate additions promoted by a chiral N-heterocyclic carbene
Brown, M. Kevin
May, Tricia L.
Baxter, Carl A.
Hoveyda, Amir H.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (07) : 1097 - 1100
[7] A practical method for enantioselective synthesis of all-carbon quaternary stereogenic centers through NHC-Cu-catalyzed conjugate additions of alkyl- and arylzinc reagents to β-substituted cyclic enones
Lee, Kang-Sang
Brown, M. Kevin
Hird, Alexander W.
Hoveyda, Amir H.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (22) : 7182 - 7184
[8] Synthesis of Quaternary Carbon Stereogenic Centers through Enantioselective Cu-Catalyzed Allylic Substitutions with Vinylaluminum Reagents
Gao, Fang
McGrath, Kevin P.
Lee, Yunmi
Hoveyda, Amir H.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (40) : 14315 - 14320
[9] Enantioselective Synthesis of Quaternary Carbon Stereogenic Centers through Copper-Catalyzed Conjugate Additions of Aryl- and Alkylaluminum Reagents to Acyclic Trisubstituted Enones
Dabrowski, Jennifer A.
Villaume, Matthew T.
Hoveyda, Amir H.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (31) : 8156 - 8159
[10] Enantioselective synthesis of all-carbon quaternary stereogenic centers by catalytic asymmetric conjugate additions of alkyl and aryl aluminum reagents to five-, six-, and seven-membered-ring β-substituted cyclic enones
May, Tricia L.
Brown, M. Kevin
Hoveyda, Amir H.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (38) : 7358 - 7362

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