Modular Cyclopentenone Synthesis through the Catalytic Molecular Shuffling of Unsaturated Acid Chlorides and Alkynes

We
describe a general strategy for the intermolecular synthesis
of polysubstituted cyclopentenones using palladium catalysis. Overall,
this reaction is achieved via a molecular shuffling process involving
an alkyne, an α,β-unsaturated acid chloride, which serves
as both the alkene and carbon monoxide source, and a hydrosilane to
create three new C–C bonds. This new carbon monoxide-free pathway
delivers the products with excellent yields. Furthermore, the regioselectivity
is complementary to conventional methods for cyclopentenone synthesis.
In addition, a set of regio- and chemodivergent reactions are presented
to emphasize the synthetic potential of this novel strategy.