Tandem carbocupration/oxygenation of terminal alkynes.
[chemical reaction: see text]. A direct and general synthesis of alpha-branched aldehydes and their enol derivatives is described. Carbocupration of terminal alkynes and subsequent oxygenation with lithium tert-butyl peroxide generates a metallo-enolate. Trapping with various electrophiles provides alpha-branched aldehydes or stereo-defined trisubstituted enol esters or silyl ethers. The tandem carbocupration/oxygenation tolerates alkyl and silyl ethers, esters, and tertiary amines. The reaction is effective with organocopper complexes derived from primary, secondary, and tertiary Grignard reagents and from n-butyllithium.
Zhang
Donghui
D
Department of Biochemistry, The University of Texas Southwestern Medical Center at Dallas, Dallas, Texas 75390-9038, USA.
Ready
Joseph M
JM
D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry; D007202:Indicators and Reagents; D010084:Oxidation-Reduction; D013237:Stereoisomerism
D000447:Aldehydes; D000480:Alkynes; D007202:Indicators and Reagents; D003300:Copper