Total synthesis of (-)-18-epi-peloruside A: an alkyne linchpin strategy.
A convergent synthetic route toward cytotoxic agent peloruside A that hinges on the use of an alkyne linchpin to assemble the natural product is described. Other highlights of this synthesis include an asymmetric desymmetrization reaction of a 1,3-diol, a one-pot conversion of a dibromoolefin to a stereodefined enone, and a diastereoselective aldol condensation. Misassignment of the absolute stereochemistry of the C18 stereocenter in our synthesis provided the natural product epimeric at the C18 ethyl stereocenter.
Department of Chemistry, Stanford University , Stanford, California 94305-5080, United States.
Barry M
BM
Trost
David J
DJ
Michaelis
Sushant
S
Malhotra
D001688:Biological Products / Q000138:chemical synthesis / Q000737:chemistry; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D013237:Stereoisomerism
D001688:Biological Products; D019086:Bridged Bicyclo Compounds, Heterocyclic; D007783:Lactones; C414085:peloruside A