Gold-catalyzed cycloisomerization of 1,5-allenynes via dual activation of an ene reaction.
Tris(triphenylphosphinegold) oxonium tetrafluoroborate, [(Ph3PAu)3O]BF4, catalyzes the rearrangement of 1,5-allenynes to produce cross-conjugated trienes. Experimental and computational evidence shows that the ene reaction proceeds through a unique nucleophilic addition of an allene double bond to a cationic phosphinegold(I)-complexed phosphinegold(I) acetylide, followed by a 1,5-hydrogen shift.
Cheong
Paul Ha-Yeon
PH
Department of Chemistry, University of California, Berkeley, California 94720, USA.
Morganelli
Philip
P
Luzung
Michael R
MR
Houk
K N
KN
Toste
F Dean
FD
D000466:Alkadienes / Q000138:chemical synthesis* / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D008956:Models, Chemical; D015394:Molecular Structure; D050607:Organogold Compounds / Q000737:chemistry*; D013237:Stereoisomerism
D000466:Alkadienes; D000480:Alkynes; D050607:Organogold Compounds