Stereoselective synthesis of vinylsilanes by a gold(I)-catalyzed acetylenic sila-cope rearrangement.
Cationic tri-tert-butylphosphinegold(I) serves as a catalyst in the sila-Cope rearrangement of acetylenic allylsilanes. When phenol is employed as a nucleophile, the reaction allows for the stereoselective synthesis of vinylsilanes. Alternatively, use of methanol as a nucleophile leads to cyclic vinylsilanes, which can be viewed as latent vinylsilanes that are revealed on treatment with a mild Lewis acid. Thus, both of these reagents serve as useful reagents for stereoselective synthesis of trisubstituted olefins through transition-metal-catalyzed cross-coupling reactions.
Horino
Yoshikazu
Y
Department of Chemistry, University of California, Berkeley, California 94720, USA.
Luzung
Michael R
MR
Toste
F Dean
FD
D000480:Alkynes / Q000737:chemistry*; D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D006046:Gold / Q000737:chemistry*; D015394:Molecular Structure; D010720:Phosphines / Q000737:chemistry; D012821:Silanes / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D000480:Alkynes; D000498:Allyl Compounds; D010720:Phosphines; D012821:Silanes; D014753:Vinyl Compounds; C476909:vinylsilane; D006046:Gold