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

doi:10.1055/s-2004-829188

PSP

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: alexandre.alexakis@chiorg.unige.ch;

Abstract

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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.

Key words

allylic substitution - copper catalysis - ruthenium catalysis - enantioselectivity - Grignard reagents

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References

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

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