Carbolithiation of diphenylacetylene as a stereoselective route to (Z)-tamoxifen and related tetrasubstituted olefins.
Carbolithiation of diphenylacetylene can be exploited to generate (E)-1-lithio-1,2-diphenylalkyl-1-enes which can be reacted in situ with triisopropylborate to stereoselectively provide (E)-1,2-diphenyl-1-alkylene boronic acids. These tetrasubstituted vinylboronic acids served as versatile intermediates for the generation of tetrasubstituted olefins with retention of stereochemistry. The application of this method for the stereoselective synthesis of (Z)-tamoxifen and related analogues is described.
McKinley
Neola F
NF
Centre for Synthesis and Chemical Biology, School of Chemistry and Chemical Biology, University College Dublin, Belfield, Dublin 4, Ireland.
O'Shea
Donal F
DF
D000114:Acetylene / Q000031:analogs & derivatives* / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D021241:Spectrometry, Mass, Electrospray Ionization; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism; D013629:Tamoxifen / Q000737:chemistry*
D000475:Alkenes; D013629:Tamoxifen; C044735:biphenylacetylene; D000114:Acetylene