title: Selective C-C and C-H bond activation/cleavage of pinene derivatives: synthesis of enantiopure cyclohexenone scaffolds and mechanistic insights.
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.
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, United States.
authors.forename: Ahmad
authors.initials: A
authors.lastname: Masarwa
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, United States.
authors.forename: Manuel
authors.initials: M
authors.lastname: Weber
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, United States.
authors.forename: Richmond
authors.initials: R
authors.lastname: Sarpong
mesh_terms: D002384:Catalysis; D003503:Cyclobutanes / Q000138:chemical synthesis / Q000737:chemistry*; D003512:Cyclohexanones / Q000138:chemical synthesis* / Q000737:chemistry; D006576:Heterocyclic Compounds, 4 or More Rings / Q000138:chemical synthesis / Q000737:chemistry; D007783:Lactones / Q000138:chemical synthesis / Q000737:chemistry; D008958:Models, Molecular; D061065:Polyketides / Q000138:chemical synthesis / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry*; D013141:Spiro Compounds / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D003503:Cyclobutanes; D003512:Cyclohexanones; D006576:Heterocyclic Compounds, 4 or More Rings; D007783:Lactones; D061065:Polyketides; D013141:Spiro Compounds; C538814:cyclobutanol; C586348:spiroindicumide A; C586349:spiroindicumide B; C413206:phomactin A; D012238:Rhodium