Palladium-catalyzed reactions of cyclohexadienones: regioselective cyclizations triggered by alkyne acetoxylation.
Regioselective cyclizations of alkyne-tethered cyclohexadienones can be accomplished under palladium catalysis. The cyclization involves an initial Pd-mediated acetoxylation of the alkyne, followed by migratory insertion and protonolysis of the resulting palladium enolate. The predictable regioselectivity of these atom-economical and stereoselective reactions is influenced by developing steric interactions during migratory insertion of a vinyl palladium intermediate.
Tello-Aburto
Rodolfo
R
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA.
Harned
Andrew M
AM
D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D053138:Cyclohexenes / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism
D000480:Alkynes; D053138:Cyclohexenes; C507608:cyclohexadienone; D010165:Palladium