Enantioselective Lactonization by π-Acid-Catalyzed Allylic Substitution: A Complement to π-Allylmetal Chemistry
Arun Raj Kizhakkayil Mangadan
Florida Center for Heterocyclic Compounds and, Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, FL, 32611 USA
Search for more papers by this authorJi Liu
Florida Center for Heterocyclic Compounds and, Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, FL, 32611 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Aaron Aponick
Florida Center for Heterocyclic Compounds and, Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, FL, 32611 USA
Search for more papers by this authorArun Raj Kizhakkayil Mangadan
Florida Center for Heterocyclic Compounds and, Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, FL, 32611 USA
Search for more papers by this authorJi Liu
Florida Center for Heterocyclic Compounds and, Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, FL, 32611 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Aaron Aponick
Florida Center for Heterocyclic Compounds and, Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, FL, 32611 USA
Search for more papers by this authorAbstract
Asymmetric allylic alkylation (AAA) is a powerful method for the formation of highly useful, non-racemic allylic compounds. Here we present a complementary enantioselective process that generates allylic lactones via π-acid catalysis. More specifically, a catalytic enantioselective dehydrative lactonization of allylic alcohols using a novel PdII-catalyst containing the imidazole-based P,N-ligand (S)-StackPhos is reported. The high-yielding reactions are operationally simple to perform with enantioselectivities up to 99 % ee. This strategy facilitates the replacement of a poor leaving group with what would ostensibly be a better leaving group in the product avoiding complications arising from racemization by equilibration.
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