Sterically Biased 3,3-Sigmatropic Rearrangement of Chiral Allylic Azides: Application to the Total Syntheses of Alkaloids
The Journal of Organic Chemistry2008Vol. 73(16), pp. 6239–6250
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Sophie Lauzon, François Tremblay, David Gagnon, Cédrickx Godbout, Christine Chabot, Catherine Mercier‐Shanks, Stéphane Perreault, Hélène DeSève, Claude Spino
Abstract
We describe a tandem Mitsunobu/3,3-sigmatropic rearrangement of allylic azides on a chiral auxiliary system that favors one regioisomer thanks to its exceptional steric bias. The sequence may be completed by the oxidative cleavage of the auxiliary or by a ring-closing metathesis reaction that produces a carbo- or heterocycle directly and a recyclable form of the chiral auxiliary. Applications of the methodology to the total synthesis of (+)-coniine, (+)-lentiginosin, and (+)-pumiliotoxin C are reported.
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