title: Nucleophile-dependent regioselective reaction of (S)-4-benzyl-2-fluoroalkyl-1,3-oxazolines.
abstract: Nucleophile-dependent regioselectivities in the nucleophilic reaction of (S)-4-benzyl-2-fluoroalkyl-1,3-oxazoline to different types of fluorinated compounds were investigated experimentally and theoretically. The ring opening of (S)-4-benzyl-2-bromodifluoromethyl-1,3-oxazoline by arenethiolates exclusively occurred at the C5 position of the 1,3-oxazoline ring, whereas completely different regioselectivity was observed for a unimolecular radical nucleophilic substitution (S(RN)1) at the terminal bromine atom of the CF2Br group when arenolates were employed as the nucleophiles. The reaction of (S)-4-benzyl-2-trifluoromethyl-1,3-oxazoline with nucleophiles such as arenethiols, arenols, and TMSCl underwent nucleophilic ring opening in a regiospecific way, while the use of TMSCF3 was determined to proceed through nucleophilic addition to the C═N bond.
authors.affiliation: Department of Chemistry, Shanghai University, 99 Shangda Road, Shanghai 200444, People's Republic of China. hzjiang@shu.edu.cn
authors.forename: Haizhen
authors.initials: H
authors.lastname: Jiang
authors.forename: Liuming
authors.initials: L
authors.lastname: Yan
authors.forename: Minjun
authors.initials: M
authors.lastname: Xu
authors.forename: Wenjun
authors.initials: W
authors.lastname: Lu
authors.forename: Yeshan
authors.initials: Y
authors.lastname: Cai
authors.forename: Wen
authors.initials: W
authors.lastname: Wan
authors.forename: Jianhua
authors.initials: J
authors.lastname: Yao
authors.forename: Shaoxiong
authors.initials: S
authors.lastname: Wu
authors.forename: Shizheng
authors.initials: S
authors.lastname: Zhu
authors.forename: Jian
authors.initials: J
authors.lastname: Hao
mesh_terms: D001593:Benzyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006845:Hydrocarbons, Fluorinated / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D010080:Oxazoles / Q000138:chemical synthesis* / Q000737:chemistry; D014961:X-Ray Diffraction
chemical_list: D001593:Benzyl Compounds; D006845:Hydrocarbons, Fluorinated; D010080:Oxazoles