ChemInform Abstract: Sterically Biased 3,3‐Sigmatropic Rearrangement of Chiral Allylic Azides: Application to the Total Syntheses of Alkaloids.

Abstract

Azides P 0095Sterically Biased 3,3-Sigmatropic Rearrangement of Chiral Allylic Azides: Application to the Total Syntheses of Alkaloids. -Treatment of allylic alcohols of type (I) with HN3 under Mitsunobu conditions leads to allylic azides which can undergo sigmatropic rearrangement to afford chiral azides of type (II). The configuration of hydroxyl group, geometry of C=C double bond, and nature of substituent R 1 play an important role on the reaction outcome. The allylic azides are versatile building blocks which can smoothly be converted into amino acids [cf. (III)] and alkaloids. -(LAUZON, S.; TREMBLAY, F.; GAGNON, D.; GODBOUT, C.; CHABOT, C.; MERCIER-SHANKS, C.; PERREAULT, S.; DESEVE, H.; SPINO*, C.; J. Org. Chem. 73 (2008) 16, 6239-6250; Dep. Chim., Fac. Sci., Univ. Sherbrooke, Sherbrooke, Que. J1K 2R1, Can.; Eng.) -Jannicke 52-060