Reductive cyclisation of ail E-vinyl bromide with ail allylic acetate proceeds under palladium catalysis 10 give the 8-dehydropumiliotoxin skeleton, a potential advanced precursor to 8-deoxypumiliotoxin alkaloids. Control of the stereochemistry of the E-vinyl bromide precursor is achieved readily using the Kogen or Bruckner bromophosphonate reagents and the reductive cyclisation proceeds with retention of the vinyl bromide stereochemistry. The mechanism for the cyclisation involves an in situ conversion of the allylic acetate to ail allyl stannane followed by ail intramolecular Stille-type coupling.
ASJC Scopus subject areas
- Organic Chemistry
- Drug Discovery
Feutran, S. A., McAlonan, H., Stevenson, P., & Walker, A. D. (2009). Palladium-mediated reductive coupling, a stereoselective approach to the 8-dehydropumiliotoxin skeleton. Tetrahedron Letters, 50(26), 3669-3671. https://doi.org/10.1016/j.tetlet.2009.03.122