Kishi, Matsuura, Peters, Anada, Harried, Hao, and Yoshito . JACS, 2006, ASAP. DOI: 10.1021/ja0618954
Kishi and co-workers have just completed their syntheses of the Pteriatoxins A-C, related to their prior work on Pinnatoxin A. Using two of the precursors developed for the latter work, they were able to create the straight-chain analogue, with the necessary addition of a third precursor. They then used a exo-selective DA to assemble the cyclohexene ring, completing the macrocycle.
The DA work in this paper is incredibly interesting – the protecting groups used on the diol influence the endo/exo selectivity massively, and also the rate of reaction, most dramatically in the case of TBS vs. Ac.
The other dramatic point in this DA was the guts it took to heat the substrate to 170 Â°C!