title: Titanium-mediated rearrangement of cyclopropenylmethyl acetates to (E)-halodienes.
abstract: TiCl(4) and TiBr(4) rapidly transform cyclopropenylmethyl acetates to (E)-halodienes via ring-opening to allyl-vinyl cations. DFT calculations suggest that the regioselectivity of the halogenation of this cationic intermediate by [TiX(4)OAc](-) is under thermodynamic control, while the stereoselectivity is governed by kinetics.
authors.affiliation: Department of Chemistry and Biochemistry, California State University, Fullerton, CA 92831, USA.
authors.forename: Gary
authors.initials: G
authors.lastname: Gallego
authors.forename: Alireza
authors.initials: A
authors.lastname: Ariafard
authors.forename: Kiet
authors.initials: K
authors.lastname: Tran
authors.forename: David
authors.initials: D
authors.lastname: Sandoval
authors.forename: Leera
authors.initials: L
authors.lastname: Choi
authors.forename: Yi-Hsun
authors.initials: YH
authors.lastname: Chen
authors.forename: Brian F
authors.initials: BF
authors.lastname: Yates
authors.forename: Fu-Ming
authors.initials: FM
authors.lastname: Tao
authors.forename: Christopher J T
authors.initials: CJ
authors.lastname: Hyland
mesh_terms: D000085:Acetates / Q000737:chemistry*; D003521:Cyclopropanes / Q000737:chemistry*; D006219:Halogens / Q000737:chemistry*; D008745:Methylation; D008958:Models, Molecular; D015394:Molecular Structure; D014025:Titanium / Q000737:chemistry*
chemical_list: D000085:Acetates; D003521:Cyclopropanes; D006219:Halogens; C021985:cyclopropene; D014025:Titanium