jo500040b_si_002.pdf (1.02 MB)

Convergent Access to Polycyclic Cyclopentanoids from α,β-Unsaturated Acid Chlorides and Alkynes through a Reductive Coupling, Nazarov Cyclization Sequence

Download (1.02 MB)
journal contribution
posted on 18.04.2014, 00:00 by Jason H. Chaplin, Kristal Jackson, Jonathan M. White, Bernard L. Flynn
Reductive coupling of α,β-unsaturated acid chlorides A with alkynoyls B provides convergent access to Nazarov cyclization precursors, α-carboxy divinyl ketones C. Cyclization of C gives an intermediate oxyallyl cation intermediate D, which can be trapped with tethered arenes (Ar). The resultant products can be further cyclized through nucleophilic displacement of suitable leaving groups X by tethered OH groups to give lactones (in a subsequent step). Where X is a suitable chiral auxiliary (e.g., oxazolidinone) this strategy affords access to homochiral cyclopentanoids.