Total synthesis and structural confirmation of (+)-longicin.
A stereocontrolled total synthesis of (+)-longicin, a representative of the class of mono-THF-acetogenins, is described. The strategy involves the utilization of d- and l-glutamic acids as chirons that correspond to two five-carbon segments harboring stereogenic centers at C4 and at C17 of the C(32) polyketide-derived natural product. The use of Grubbs' RCM reaction as a novel "chain elongation" strategy for the synthesis of acetogenin-type structures and a new protocol for butenolide incorporation are also described. [structure: see text]
Hanessian
Stephen
S
Department of Chemistry, Université de Montréal, C.P. 6128, Succursale Centre-Ville, Montréal, Québec H3C 3J7, Canada. stephen.hanessian@umontreal.ca
Giroux
Simon
S
Buffat
Maxime
M
D015107:4-Butyrolactone / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D029061:Annonaceae / Q000737:chemistry; D002384:Catalysis; D015394:Molecular Structure; D013237:Stereoisomerism
C096944:longicin; D015107:4-Butyrolactone