Synthesis 2004(15): 2586-2590  
DOI: 10.1055/s-2004-829188
PSP
© Georg Thieme Verlag Stuttgart · New York

Synthesis and Use of a Phosphoramidite Ligand for the Copper-Catalyzed Enantioselective­ Allylic Substitution. Tandem Allylic Substitution/Ring-Closing­ Metathesis

Karine Tissot-Croset, Damien Polet, Ségolène Gille, Christine Hawner, Alexandre Alexakis*
Department of Organic Chemistry, University of Geneva, 30 quai Ernest-Ansermet, 1211 Genève 4, Switzerland
Fax: +41(22)3793215; e-Mail: [email protected];
Further Information

Publication History

Received 26 April 2004
Publication Date:
30 July 2004 (online)

Abstract

A new one-pot method of reductive amination is used to prepare a chiral C2 symmetrical amine. This amine is used for the synthesis of a new chiral phosphoramidite ligand. The new ligand is, in turn, used to illustrate the enantioselective copper-catalyzed allylic substitution with Grignard reagents. When a remote double bond is located on the Grignard reagent, the newly formed alkene undergoes an in situ ruthenium-catalyzed ring-closing metathesis to afford the cyclized product in 77% yield and 94% ee.

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