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Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs
Published on: January 17, 2020
Lactone Synthesis by Enantioselective Orthogonal Tandem Catalysis
Sourabh Mishra1, Aaron Aponick1
1Florida Center for Heterocyclic Compounds and Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, FL, 32607, USA.
Abstract:
In this work, we report enantioselective orthogonal tandem catalysis for the one pot conversion of Meldrum's acid derivatives and alkynes into δ-lactones. This new transformation, which resembles a formal [4+2] cycloaddition with concomitant decarboxylation and loss of acetone, proceeds in high yields and excellent enantioselectivity (up to 99 % ee) over a broad substrate scope. The products are densely functionalized and ripe for further transformations, as demonstrated here by both ring-opening reactions and reduction to saturated lactones. It was discovered that a new and serendipitously formed AgI -Me-StackPhos complex efficiently catalyzes the highly selective 6-endo-dig cyclization, completely reversing the regiochemistry that has been previously reported in related systems. More generally, in this study we identify a pair of compatible catalysts for alkyne difunctionalization that operate concurrently, which enable the alkyne to act as both a nucleophile and an electrophile in sequential one-pot transformations.
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