Enantioselective and Diastereodivergent Allylation of Propargylic C–H Bonds
Jin Zhu, Yidong Wang, Yidong Wang, Aaron D. Charlack, Yiming Wang, Yiming Wang
Abstract
An iridium-catalyzed stereoselective coupling of allylic ethers and alkynes to generate 3,4-substituted 1,5-enynes is reported. Under optimized conditions, the coupling products are formed with excellent regio-, diastereo-, and enantioselectivities, and the protocol is functional group tolerant. Moreover, we report conditions that allow the reaction to proceed with complete reversal of diastereoselectivity. Mechanistic studies are consistent with an unprecedented dual role for the iridium catalyst, enabling the propargylic deprotonation of the alkyne through π-coordination, as well as the generation of a π-allyl species from the allylic ether starting material.
Topics & Concepts
ChemistryAllylic rearrangementAlkyneIridiumStereoselectivityDeprotonationEnantioselective synthesisCatalysisRegioselectivityEtherCombinatorial chemistryMedicinal chemistryStereochemistryOrganic chemistryIonCatalytic C–H Functionalization MethodsCatalytic Cross-Coupling ReactionsCatalytic Alkyne Reactions