title: Chiral Brønsted Acid as a True Catalyst: Asymmetric Mukaiyama Aldol and Hosomi-Sakurai Allylation Reactions.
abstract: Highly diastereo- and enantioselective Mukaiyama aldol reaction catalyzed by a new chiral Brønsted acid, N-(perfluorooctanesulfonyl)thiophosphoramide, is described. The perfluorooctyl substituent on the sulfonyl group of the catalyst plays an essential role in the stereoselection. The catalyst also allows the asymmetric Hosomi-Sakurai allylation, which has been considerably challenging due to the low reactivity of allylsilanes. (29)Si and (31)P NMR monitoring reveals the characteristic feature of the thiophosphoramide catalyst, acting as a strong Brønsted acid even in the presence of excess silyl nucleophiles, which cannot be found in other related phosphoric acid analogues.
authors.affiliation: Molecular Catalyst Research Center, Chubu University, 1200 Matsumoto-cho, Kasugai, Aichi 487-8501, Japan.
authors.forename: Masahiro
authors.initials: M
authors.lastname: Sai
authors.affiliation: Molecular Catalyst Research Center, Chubu University, 1200 Matsumoto-cho, Kasugai, Aichi 487-8501, Japan.
authors.forename: Hisashi
authors.initials: H
authors.lastname: Yamamoto
mesh_terms: D000143:Acids / Q000737:chemistry*; D000478:Alkylation; D002384:Catalysis; D013237:Stereoisomerism
chemical_list: D000143:Acids