title: Efficient Access to Multifunctional Trifluoromethyl Alcohols through Base-Free Catalytic Asymmetric C-C Bond Formation with Terminal Ynamides.
abstract: The asymmetric addition of terminal ynamides to trifluoromethyl ketones with a readily available chiral zinc catalyst gives CF3 -substituted tertiary propargylic alcohols in up to 99 % yield and 96 % ee. The exclusion of organozinc additives and base as well as the general synthetic utility of the products are key features of this reaction. The value of the β-hydroxy-β-trifluoromethyl ynamides is exemplified by selective transformations to chiral Z- and E-enamides, an amide, and N,O-ketene acetals. The highly regioselective hydration, stereoselective reduction, and hydroacyloxylation reactions proceed with high yields and without erosion of the ee value of the parent β-hydroxy ynamides.
authors.affiliation: Department of Chemistry, Georgetown University, 37th and O Streets, Washington, DC, 20057, USA.
authors.forename: Andrea M
authors.initials: AM
authors.lastname: Cook
authors.affiliation: Department of Chemistry, Georgetown University, 37th and O Streets, Washington, DC, 20057, USA. cw27@georgetown.edu.
authors.forename: Christian
authors.initials: C
authors.lastname: Wolf
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D000577:Amides / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D008958:Models, Molecular; D014961:X-Ray Diffraction
chemical_list: D000438:Alcohols; D000577:Amides; D002244:Carbon
keywords: enamides; homogeneous catalysis; organofluorine compounds; synthetic methods; ynamides