title: DFT Studies on the Stereoselectivity of α-Silyloxy Diazoalkane Cycloadditions.
abstract: The intramolecular [3+2] cycloaddition (32CA) of alkene-tethered α-silyloxydiazoalkanes provides variable stereoselectivity in generating bicyclic pyrazolines where the silyloxy group is either syn or anti to the newly formed pyrazoline ring. To elucidate the origin of the stereoselectivity, density functional theory (DFT) calculations were carried out for the energy of each transition state structure (TSs) and product. Steric effects were identified as the major determining factors in the diastereoselectivity of the 32CA reaction with regards to substrate structure (cyclic or acyclic α-silyloxydiazoalkanes).
authors.affiliation: Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago 60607, IL, USA. moconn26@uic.edu.
authors.forename: Matthew J
authors.initials: MJ
authors.lastname: O'Connor
authors.affiliation: Abbvie Inc., 1 North Waukegan Road, North Chicago 60064, IL, USA. huaqing.liu@abbvie.com.
authors.forename: Huaqing
authors.initials: H
authors.lastname: Liu
authors.affiliation: Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago 60607, IL, USA. dsunglee@uic.edu.
authors.forename: Daesung
authors.initials: D
authors.lastname: Lee
authors.affiliation: College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325035, China. xyz@wzu.edu.cn.
authors.forename: Tao
authors.initials: T
authors.lastname: Zhou
authors.affiliation: College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325035, China. xyz@wzu.edu.cn.
authors.forename: Yuanzhi
authors.initials: Y
authors.lastname: Xia
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D003500:Cyclization; D061565:Cycloaddition Reaction; D015394:Molecular Structure; D017646:Organosilicon Compounds / Q000737:chemistry*; D011720:Pyrazoles / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D017646:Organosilicon Compounds; D011720:Pyrazoles
keywords: [3+2] cycloaddition; density functional theory; diazoalkane; gauche effect; stereoselectivity