The Catalytic Asymmetric Mukaiyama–Michael Reaction of Silyl Ketene Acetals with Cyclic Enones: Short Routes to Jasmonates
Year: 2026
Type: article
Abstract: A silylium imidodiphosphorimidate (IDPi) Lewis acid catalyst enables a broadly applicable organocatalytic asymmetric Mukaiyama-Michael addition of moderately electrophilic cycloenones with enol silanes, affording 1,4-adducts in up to 98% yield and >99:1 e.r. At 0.05 mol % catalyst loading, the reaction scales to 167 g of product with 96% catalyst recovery. The method accommodates a wide range of enones and silylated nucleophiles, allowing streamlined access to key jasmonates and related valuable targets. Computational studies elucidated the origin of the enantioselectivity in this reaction. This platform thus provides a versatile entry to structurally complex chiral scaffolds with direct relevance to plant signaling, fragrance chemistry, aromatherapy, and pharmaceutical sciences.
DOI: 10.1021/jacs.5c20804
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W7128905362