Total Synthesis of Pikronolide

Yonemitsu s pikronolide synthesis is based on the coupling of the C -Ciq (123) and C11-C13 (30) segments derived from D-glucose, and the effective application of benzyl type protecting groups, MPM (4-methoxybenzyl) and DMPM (3,4-dimethoxybenzyl), which were developed by his group for the macrolide synthesis. [Pg.15]

The compounds 26 and 30 were also used for his methynolide synthesis. The aldehyde derived from 26 reacted with crotyltributylstannane to give stereoselectively 121, which was selectively protected to the alcohol 122. This alcohol was transformed into the ketophosphonate carboxylic acid 123. Yamaguchi esterification of 30 with 123 gave the corresponding ester, which was cyclized by Nicolaou method to give the 14-membered enone 124. Selective deprotection of the DMPM group with DDQ followed by Swem s oxidation [Pg.15]

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