title: Mechanisms of the InCl3-catalyzed type-I, II, and III cycloisomerizations of 1,6-enynes.
abstract: InCl3-catalyzed cycloisomerizations of 1,6-enynes can give either type-I dienes and cyclohexenes (type-III dienes), or type-II dienes, depending on the substitutions in the substrates. Previously, we studied how the type-II diene products were generated and found that the real catalytic species for the cycloisomerizations is InCl2(+) (J. Org. Chem. 2012, 77, 8527-8540). In the present paper, we used density functional theory (DFT) calculations to reveal how the type-I and type-III dienes were generated. A unified model to explain how substituents affect the regiochemistry of type-I, II, and III cycloisomerizations has been provided. Experimental and computational investigation of the InCl3-catalyzed cycloisomerization of 1,6-enynes with both substituents at the alkyne and alkene parts has also been reported in the present study.
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University , Beijing 100871, China.
authors.forename: Lian-Gang
authors.initials: LG
authors.lastname: Zhuo
authors.forename: Ji-Ji
authors.initials: JJ
authors.lastname: Zhang
authors.forename: Zhi-Xiang
authors.initials: ZX
authors.lastname: Yu