title: The influence of perfluorinated substituents on the nucleophilic reactivities of silyl enol ethers.
abstract: The fluorinated trimethylsilyl enol ethers 3a-c were synthesized, and the kinetics of their reactions with the benzhydrylium ions 4 was studied by UV-vis spectroscopy in dichloromethane. Comparison with nonfluorinated analogues shows that replacement of CH(3) by CF(3) reduces the nucleophilic reactivity by 8 orders of magnitude, while the exchange of C(6)H(5) by C(6)F(5) retards the reactions by 4.5 orders of magnitude.
authors: Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13 (Haus F), 81377 München, Germany.
authors: Hans A
authors: HA
authors: Laub
authors: Daniel
authors: D
authors: Gladow
authors: Hans-Ulrich
authors: HU
authors: Reissig
authors: Herbert
authors: H
authors: Mayr
mesh_terms: D004987:Ethers / Q000138:chemical synthesis* / Q000737:chemistry; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D007700:Kinetics; D015394:Molecular Structure; D056951:Photoelectron Spectroscopy; D014297:Trimethylsilyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D004987:Ethers; D006845:Hydrocarbons, Fluorinated; D014297:Trimethylsilyl Compounds