Abstract
A stereoselective synthesis of the C1–C13 segment of poecillastrin C has been achieved.
The C1–C4 moiety was derived from diallyl l-tartrate, and the amide group at the C3 position was constructed by means of a traceless
Staudinger reaction. The C1–C13 segment was submitted to model studies, including
esterification with a bulky alcohol at the C1 position and Stille coupling with vinyl
iodide at the C13 position. The reactivity of the C1 position was affected by the
neighboring C2-protective group. When the C2 hydroxy group was protected as a TBS
ether, the C1 carboxylic acid did not undergo esterification with a bulky secondary
alcohol, whereas the p-methoxybenzylidene N,O-acetal afforded a 2,4-dimethyl-3-pentyl ester. Stille coupling of the C1–C13 segment
with 1-iodohept-1-ene gave the southern part of the poecillastrin C macrolactam attached
to simplified eastern and western parts.
Key words
stereoselective synthesis - hydroxyaspartic acid - Staudinger reaction - poecillastrin