Rhodium‐Catalyzed Asymmetric [2+2+2] Cycloaddition of 1,6‐Enynes with Racemic Secondary Allylic Alcohols through Kinetic Resolution
Shunsuke Suzuki, Yu Shibata, Ken Tanaka
Abstract
It has been established that a cationic rhodium(I)/P-phos complex catalyzes the asymmetric [2+2+2] cycloaddition of 1,6-enynes with racemic secondary allylic alcohols to produce the corresponding chiral bicyclic cyclohexenes, possessing three stereogenic centers, as a single diastereomer with excellent ee values. Mechanistic experiments revealed that the present cycloaddition proceeds through the kinetic resolution of the racemic secondary allylic alcohols, in which one enantiomer preferentially reacts with the 1,6-enyne.
Topics & Concepts
Kinetic resolutionAllylic rearrangementStereocenterCycloadditionChemistryEnyneRhodiumDiastereomerEnantiomerCationic polymerizationStereochemistryEnantioselective synthesisBicyclic moleculeCatalysisMedicinal chemistryOrganic chemistrySynthetic Organic Chemistry MethodsCatalytic Alkyne ReactionsCatalytic C–H Functionalization Methods