Enantioselective Ruthenium-BINAP-Catalyzed Carbonyl Reductive Coupling of Alkoxyallenes: Convergent Construction of <i>syn-sec,tert</i>-Diols via (<i>Z</i>)-σ-Allylmetal Intermediates
Ming Xiang, Dana E. Pfaffinger, Eliezer Ortiz, Gilmar A. Brito, Michael J. Krische
Abstract
The first catalytic enantioselective ruthenium-catalyzed carbonyl reductive couplings of allene pronucleophiles is described. Using an iodide-modified ruthenium-BINAP-catalyst and O-benzhydryl alkoxyallene 1a, carbonyl (α-alkoxy)allylation occurs from the alcohol or aldehyde oxidation level to form enantiomerically enriched syn-sec,tert-diols. Internal chelation directs intervention of (Z)-σ-alkoxyallylruthenium isomers, which engage in stereospecific carbonyl addition.
Topics & Concepts
ChemistryRutheniumEnantioselective synthesisBINAPAldehydeCatalysisAlkoxy groupIodideMedicinal chemistryAlleneStereochemistryOrganic chemistryAlkylAsymmetric Hydrogenation and CatalysisCatalytic C–H Functionalization MethodsAsymmetric Synthesis and Catalysis