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Ladder Polyether Synthesis via Epoxide-Opening Cascades Using a Disappearing Directing Group

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journal contribution
posted on 01.02.2006, 00:00 by Graham L. Simpson, Timothy P. Heffron, Estíbaliz Merino, Timothy F. Jamison
The combination of a trimethylsilyl group, a Brønsted base, a fluoride source, and a hydroxylic solvent enables the first construction of the tetrad of tetrahydropyran rings found in the majority of the ladder polyether natural products by way of a cascade of epoxide-opening events that emulates the final step of Nakanishi's proposed biosynthetic pathway. The trimethylsilyl group disappears during the course of the cascade, and thus these are the first epoxide ring-opening cascades that afford ladder polyether subunits containing no directing groups at the end of the cascade.