# The Catalytic Asymmetric Mukaiyama–Michael Reaction of Silyl Ketene Acetals with Cyclic Enones: Short Routes to Jasmonates

## TL;DR

A new catalyst enables efficient and selective synthesis of jasmonates, important compounds in plant signaling and fragrance chemistry.

## Contribution

A silylium imidodiphosphorimidate catalyst enables high-yield, enantioselective Mukaiyama–Michael reactions for streamlined jasmonate synthesis.

## Key findings

- The reaction achieves up to 98% yield and >99:1 enantiomeric ratio with 0.05 mol% catalyst loading.
- The method allows scalable synthesis of jasmonates and related compounds with high enantioselectivity.
- Computational studies explain the origin of the observed enantioselectivity.

## 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.