Biomimetic syntheses of (-)-gochnatiolides A-C and (-)-ainsliadimer B.
We report the first biomimetic syntheses of (-)-gochnatiolides A-C and (-)-ainsliadimer B based on our proposed biogenetic pathway. Our synthesis features one-pot cascade transformations including Saegusa oxidation, intermolecular Diels-Alder cycloaddition, and radical-mediated allylic oxidation, which allow for the rapid generation of (-)-gochnatiolides A-C in a collective manner. We also disclose an unprecedented "copper effect" on the stereochemical outcome of the radical-mediated allylic oxidation. Our synthetic endeavors led to the structural reassignment of (-)-gochnatiolide B. Ultimately, a biomimetic transformation from gochnatiolide B to ainsliadimer B was achieved through a remarkable direct enone hydration.
College of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, China.
Chao
C
Li
Longyang
L
Dian
Weidong
W
Zhang
Xiaoguang
X
Lei
D019659:Asteraceae / Q000737:chemistry*; D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D032701:Biomimetics / Q000379:methods*; D060326:Chemistry Techniques, Synthetic / Q000379:methods*; D057930:Click Chemistry / Q000379:methods; D020650:Combinatorial Chemistry Techniques / Q000379:methods; D018360:Crystallography, X-Ray; D061565:Cycloaddition Reaction / Q000379:methods; D019281:Dimerization; D008958:Models, Molecular; D010084:Oxidation-Reduction; D012717:Sesquiterpenes / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D001688:Biological Products; D012717:Sesquiterpenes