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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

Supporting Info

Kang-sang Lee, M. Kevin Brown, Alexander W. Hird, and Amir H. Hoveyda*

Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467

J. Am. Chem. Soc., 2006, 128 (22), pp 7182–7184

DOI: 10.1021/ja062061o

Publication Date (Web): May 13, 2006

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, amir.hoveyda@bc.edu

Abstract

We present the first examples of Cu-catalyzed enantioselective conjugate additions of alkyl- and arylzinc reagents to unactivated cyclic β-substituted enones. Transformations are promoted in the presence of 2.5−15 mol % of a readily available chiral NHC-based Cu complex, affording the desired products bearing all-carbon quaternary stereogenic centers in 67→98% yield and in up to 97% ee. Catalytic enantioselective reactions can be carried out on a benchtop, with undistilled solvent and commercially available (not further purified) Cu salts. Mechanistic models, accounting for the observed levels and trends in enantioselectivity are provided.

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Published In Issue June 07, 2006
Received April 5, 2006

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Communication

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

Abstract

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SciFinder Links

History

Recommend & Share

Related Content

Copper-Catalyzed Asymmetric Conjugate Addition of Grignard Reagents to Trisubstituted Enones. Construction of All-Carbon Quaternary Chiral Centers Copper-Catalyzed Asymmetric Conjugate Addition of Grignard Reagents to Trisubstituted Enones. Construction of All-Carbon Quaternary Chiral Centers

Bidentate NHC-Based Chiral Ligands for Efficient Cu-Catalyzed Enantioselective Allylic Alkylations: Structure and Activity of an Air-Stable Chiral Cu Complex

A Readily Available Chiral Ag-Based N-Heterocyclic Carbene Complex for Use in Efficient and Highly Enantioselective Ru-Catalyzed Olefin Metathesis and Cu-Catalyzed Allylic Alkylation Reactions

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