Stereo‐ and Site‐Selective Crotylation of Alcohol Proelectrophiles via Ruthenium‐Catalyzed Hydrogen Auto‐Transfer Mediated by Methylallene and Butadiene
Eliezer Ortiz, Brian J. Spinello, Yoon Cho, Jessica Wu, Michael J. Krische
Abstract
Iodide-bound ruthenium-JOSIPHOS complexes catalyze the redox-neutral C-C coupling of primary alcohols with methylallene (1,2-butadiene) or 1,3-butadiene to form products of anti-crotylation with good to excellent levels of diastereo- and enantioselectivity. Distinct from other methods, direct crotylation of primary alcohols in the presence of unprotected secondary alcohols is possible, enabling generation of spirastrellolide B (C9-C15) and leucascandrolide A (C9-C15) substructures in significantly fewer steps than previously possible.
Topics & Concepts
RutheniumAlcoholCatalysisChemistryAlcohol oxidationTransfer hydrogenationRedoxHydrogen1,3-ButadieneCombinatorial chemistryIodideStereochemistryOrganic chemistryAsymmetric Hydrogenation and CatalysisSynthetic Organic Chemistry MethodsCatalytic C–H Functionalization Methods