De novo asymmetric synthesis of cladospolide B-D: structural reassignment of cladospolide D via the synthesis of its enantiomer.
The enantioselective synthesis of cladospolide B, C, and (ent)-cladospolide D has been achieved in 11-15 steps from 1-nonyne. The route relies upon an alkyne zipper reaction to relay an ynone and dienoate functional groups across a nine carbon fragment, which enables a highly enantioselective Noyori ynone reduction and a diastereo- and regioselective Sharpless dihydroxylation of a dienoate. In addition to being a flexible approach to three members of the cladospolide natural products, this route for the first time correctly established the structure for cladospolide D.
Xing
Yalan
Y
Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506, USA.
O'Doherty
George A
GA
D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D002963:Cladosporium / Q000737:chemistry; D018942:Macrolides / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism
D001688:Biological Products; D018942:Macrolides; C437366:cladospolide D; C492940:cladospolide B; C492938:cladospolide C