title: Enantioselective electrophilic trifluoromethylthiolation of β-ketoesters: a case of reactivity and selectivity bias for organocatalysis.
abstract: A chiral Lewis base or a phase-transfer catalyst (PTC) can mediate the highly enantioselective trifluoromethylthiolation of β-ketoesters with the previously developed SCF3 reagent. Reactions of indanone-derived β-ketoesters occurred with high yield and excellent enantioselectivity with quinine as catalyst. Reactions of tetralone- or 1-benzosuberone-derived β-ketoesters occurred with moderate to good enantioselectivity with a quinine-derived PTC.
authors.affiliation: Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China).
authors.forename: Xueqiang
authors.initials: X
authors.lastname: Wang
authors.forename: Tao
authors.initials: T
authors.lastname: Yang
authors.forename: Xiaolin
authors.initials: X
authors.lastname: Cheng
authors.forename: Qilong
authors.initials: Q
authors.lastname: Shen
mesh_terms: D002384:Catalysis; D018360:Crystallography, X-Ray; D004952:Esters / Q000737:chemistry*; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry; D007189:Indans / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D011803:Quinine / Q000737:chemistry; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D004952:Esters; D006845:Hydrocarbons, Fluorinated; D007189:Indans; D007659:Ketones; D013438:Sulfhydryl Compounds; D011803:Quinine
keywords: asymmetric synthesis; fluorine; organocatalysis; quinine; trifluoromethylthiolation