title: Asymmetric 1,2-perfluoroalkyl migration: easy access to enantioenriched α-hydroxy-α-perfluoroalkyl esters.
abstract: This study has led to the development of a novel, highly efficient, 1,2-perfluoro-alkyl/-aryl migration process in reactions of hydrate of 1-perfluoro-alkyl/-aryl-1,2-diketones with alcohols, which are promoted by a Zn(II)/bisoxazoline and form α-perfluoro-alkyl/-aryl-substituted α-hydroxy esters. With (-)-8-phenylmenthol as the alcohol, the corresponding menthol esters are generated in high yields with excellent levels of diastereoselectivity. The mechanistic studies show that the benzilic ester-type rearrangement reaction takes place via an unusual 1,2-migration of electron-deficient trifluoromethyl group rather than the phenyl group. The overall process serves as a novel, efficient, and simple approach for the synthesis of highly enantioenriched, biologically relevant α-hydroxy-α-perfluoroalkyl carboxylic acid derivatives.
authors: †State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
authors: Pan
authors: P
authors: Wang
authors: †State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
authors: Liang-Wen
authors: LW
authors: Feng
authors: †State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
authors: Lijia
authors: L
authors: Wang
authors: †State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
authors: Jun-Fang
authors: JF
authors: Li
authors: †State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
authors: Saihu
authors: S
authors: Liao
authors: †State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.|‡Collaborative Innovation Center of Chemical Science and Engineering (Tianjin).
authors: Yong
authors: Y
authors: Tang
mesh_terms: D000438:Alcohols / Q000737:chemistry; D002384:Catalysis; D003510:Cyclohexanes / Q000737:chemistry; D004952:Esters; D005466:Fluorocarbons / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry; D008610:Menthol / Q000031:analogs & derivatives / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: C435306:8-phenylmenthol; D000438:Alcohols; D003510:Cyclohexanes; D004952:Esters; D005466:Fluorocarbons; D007659:Ketones; D008610:Menthol