Organocatalytic Synthesis of α-Trifluoromethyl Allylboronic Acids by Enantioselective 1,2-Borotropic Migration
Sybrand J. T. Jonker, Ramasamy Jayarajan, Tautvydas Kireilis, Marie Deliaval, Lars Eriksson, Kálmán J. Szabó
Abstract
/TMS-diazomethanes in the presence of BINOL catalyst and ethanol. The chiral α-substituted allylboronic acids were reacted with aldehydes or oxidized to alcohols in situ with a high degree of chirality transfer. The oxygen-sensitive allylboronic acids can be purified via their isolated diaminonaphthalene (DanH)-protected derivatives. The highly reactive purified allylboronic acids reacted in a self-catalyzed reaction at room temperature with ketones, imines, and indoles to give congested trifluoromethylated homoallylic alcohols/amines with up to three contiguous stereocenters.
Topics & Concepts
ChemistryStereocenterEnantioselective synthesisCatalysisTrifluoromethylChirality (physics)OrganocatalysisOrganic chemistryAmino acidCombinatorial chemistryBiochemistryPhysicsNambu–Jona-Lasinio modelAlkylQuantum mechanicsQuarkChiral symmetry breakingFluorine in Organic ChemistryAsymmetric Synthesis and CatalysisCyclopropane Reaction Mechanisms