Selective C–C and C–H Bond Activation/Cleavage of Pinene Derivatives: Synthesis of Enantiopure Cyclohexenone Scaffolds and Mechanistic Insights
- Authors
- Type
- Published Article
- Journal
- Journal of the American Chemical Society
- Publisher
- American Chemical Society
- Publication Date
- May 13, 2015
- Volume
- 137
- Issue
- 19
- Identifiers
- DOI: 10.1021/jacs.5b02254
- PMID: 25892479
- Source
- CCHF
- License
- White
Abstract
The continued development of transition-metal-mediated C-C bond activation/cleavage methods would provide even more opportunities to implement novel synthetic strategies. We have explored the Rh(I)-catalyzed C-C activation of cyclobutanols resident in hydroxylated derivatives of pinene, which proceed in a complementary manner to the C-C bond cleavage that we have observed with many traditional electrophilic reagents. Mechanistic and computational studies have provided insight into the role of C-H bond activation in the stereochemical outcome of the Rh-catalyzed C-C bond activation process. Using this new approach, functionalized cyclohexenones that form the cores of natural products, including the spiroindicumides and phomactin A, have been accessed.