title: Enantioselective rhodium/ruthenium photoredox catalysis en route to chiral 1,2-aminoalcohols.
abstract: A rhodium-based chiral Lewis acid catalyst combined with [Ru(bpy)3](PF6)2 as a photoredox sensitizer allows for the visible-light-activated redox coupling of α-silylamines with 2-acyl imidazoles to afford, after desilylation, 1,2-amino-alcohols in yields of 69-88% and with high enantioselectivity (54-99% ee). The reaction is proposed to proceed via an electron exchange between the α-silylamine (electron donor) and the rhodium-chelated 2-acyl imidazole (electron acceptor), followed by a stereocontrolled radical-radical reaction. Substrate scope and control experiments reveal that the trimethylsilyl group plays a crucial role in this reductive umpolung of the carbonyl group.
authors.affiliation: Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35043 Marburg, Germany. meggers@chemie.uni-marburg.de.
authors.forename: Jiajia
authors.initials: J
authors.lastname: Ma
authors.affiliation: Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35043 Marburg, Germany. meggers@chemie.uni-marburg.de.
authors.forename: Klaus
authors.initials: K
authors.lastname: Harms
authors.affiliation: Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35043 Marburg, Germany. meggers@chemie.uni-marburg.de and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China.
authors.forename: Eric
authors.initials: E
authors.lastname: Meggers
mesh_terms: D000605:Amino Alcohols / Q000737:chemistry* / Q000378:metabolism; D002384:Catalysis; D010084:Oxidation-Reduction; D055668:Photochemical Processes; D012238:Rhodium / Q000737:chemistry* / Q000378:metabolism; D012428:Ruthenium / Q000737:chemistry* / Q000378:metabolism; D013237:Stereoisomerism
chemical_list: D000605:Amino Alcohols; D012428:Ruthenium; D012238:Rhodium