title: Synthetic and mechanistic studies of the cycloisomerization and cyclization/hydrosilylation of functionalized dienes catalyzed by cationic palladium(II) complexes.
abstract: This Account describes the development and mechanistic study of the cycloisomerization and cyclization/hydrosilylation of functionalized dienes catalyzed by cationic palladium(II) complexes. These transformations are characterized by good functional group compatibility, high regio- and stereoselectivity, and low air- and moisture-sensitivity. Mechanistic studies of palladium phenanthroline-catalyzed diene cycloisomerization and cyclization/hydrosilylation established mechanisms involving C-C bond formation via intramolecular carbometalation of an alkyl olefin chelate complex, which was directly observed in the context of cyclization/hydrosilylation.
authors.affiliation: P. M. Gross Chemical Laboratory, Duke University, Durham, North Carolina 27708-0346, USA.
authors.forename: Ross A
authors.initials: RA
authors.lastname: Widenhoefer
mesh_terms: D002384:Catalysis; D003500:Cyclization; D006844:Hydrocarbons, Cyclic / Q000138:chemical synthesis* / Q000737:chemistry; D007536:Isomerism; D015394:Molecular Structure; D017646:Organosilicon Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010165:Palladium / Q000737:chemistry; D010618:Phenanthrolines / Q000737:chemistry
chemical_list: D006844:Hydrocarbons, Cyclic; D017646:Organosilicon Compounds; D010618:Phenanthrolines; D010165:Palladium