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Synfacts 2006(2): 0128-0128
DOI: 10.1055/s-2005-924783
DOI: 10.1055/s-2005-924783
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York
Tandem Carbocupration/Oxygenation of Terminal Alkynes
D. Zhang, J. M. Ready*
The University of Texas Southwestern Medical Center at Dallas, USA
Further Information
Publication History
Publication Date:
23 January 2006 (online)

Significance
α-Branched aldehydes were synthesized via a tandem carbocupration of terminal alkynes followed by sequential oxygenation of the intermediate vinyl copper species with lithium tert-butyl peroxide. Trapping the metal enolate with TMSCl, acetic anhydride or benzoic anhydride gave the corresponding enol derivatives as a single regio- and stereoisomer. Addition of Br2 or t-BuOCl to the intermediate metallo-enolate generated the α-haloaldehyde. Functional groups tolerated include esters, silyl ethers, benzyl ethers, and tertiary amines. The reaction was successful using primary, secondary and tertiary Grignard reagents and also n-butyllithium.