Total synthesis of (-)-apicularen A.
A convergent total synthesis of (-)-apicularen A, a highly cytostatic 12-membered macrolide, has been accomplished. The key steps include assembling of iodoalkene 8 and aldehyde 9 by Nozaki-Hiyama-Kishi (NHK) coupling, stereospecific construction of 2,6-trans-disubstituted dihydropyran by Pd(II)-catalyzed 1,3-chirality transfer reaction, and Yamaguchi macrolactonization. Introduction of the (2Z,4Z)-heptadienamide moiety in the side chain by an efficient Cu(I)-mediated coupling completed the total synthesis.
Palimkar
Sanjay S
SS
Kyoto Pharmaceutical University, Misasagi Yamashina, Kyoto 607-8412, Japan.
Uenishi
Jun'ichi
J
D000447:Aldehydes / Q000737:chemistry; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis*; D003300:Copper / Q000737:chemistry; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D015394:Molecular Structure
D000447:Aldehydes; D019086:Bridged Bicyclo Compounds, Heterocyclic; C117813:apicularen A; D003300:Copper