Yohei Kiyotsuka

A study toward a total synthesis of fostriecin

Abstract In order to synthesize the major C(3)C(12) part of fostriecin, asymmetric dihydroxylation of several dienes 5a – f , prepared by cross-coupling reactions of several types, was studied, thus providing high dependency on the hydroxyl groups at C(5) and C(11). The best regioselectivity was obtained with 5d to produce diol 23 , which was later transformed into the advanced intermediate 26 .

Site-recognition of one of the two alkoxy carbonyl groups present in the dienophile for Diels–Alder reaction

Abstract Recognition of one alkoxy carbonyl group from the two in a molecule by a Lewis acid was investigated using 1a – e in the Diels–Alder reaction with diene 6 . Combination of 1a and BF 3 ·OEt 2 provided the highest efficiency to afford 7a , thus showing evidence for the site-selective coordination of BF 3 ·OEt 2 to the MOM-oxy carbonyl group in 1a . Furthermore, the generality and high reactivity of this combination were confirmed with dienes 11 – 14 .