Enantioselective organo-SOMO cascade cycloadditions: a rapid approach to molecular complexity from simple aldehydes and olefins.
A highly selective, radical-mediated (4 + 2) coupling reaction of aldehydes and conjugated olefins has been achieved through asymmetric SOMO-catalysis. A radical-polar crossover mechanism is proposed wherein olefin addition to a transient enamine radical cation and oxidation of the resulting radical furnishes a cation which is vulnerable to nucleophilic addition. A range of aromatic aldehydes are shown to couple with styrenes and dienes to provide cyclic products with high chemical efficiency, regioselectivity, and stereoselectivity.
Jui
Nathan T
NT
Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, USA.
Lee
Esther C Y
EC
MacMillan
David W C
DW
D000447:Aldehydes / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D001688:Biological Products / Q000737:chemistry; D002384:Catalysis; D003510:Cyclohexanes / Q000737:chemistry; D007700:Kinetics; D013237:Stereoisomerism; D013379:Substrate Specificity
D000447:Aldehydes; D000475:Alkenes; D001688:Biological Products; D003510:Cyclohexanes; C506365:Cyclohexane