Enantioselective intermolecular gold-catalysis is challenging, because the linear coordination geometry of Au(I) complexes imposes the approach of pronucleophiles from the opposite side of the gold. Prompted by our recent success in promoting intermolecular enantioselective coupling of propiolates and alkenes, we embarked on the enantioselective alkoxylation and thioallylation of propiolates, via [3,3]-sigmatropic rearrangement. The substate scope of enantioselective Claisen rearrangement has been limited to a few systems and we introduced herein use of -onium intermediates for the enantioselective Claisen rearrangement for the first time. Remarkably, by replacing allyl ethers with allyl thioethers, problems such as dissociation of allyl unit (<b>A</b>) and competing [1,3]-rearrangement (<b>B</b>) could be minimized. Thus, the current Au(I)-catalyzed thioallylation allows for remarkable scope of allyl group, including highly enantioselective synthesis of all C-quaternary centers and exceptional functional group compatibility with many Lewis bases and π-groups.

Catalytic asymmetric thioallylation of propiolates via charge-induced thio-Claisen rearrangement

ACS Spring Meeting 2021

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