Sterically Biased 3,3-Sigmatropic Rearrangement of Chiral Allylic Azides: Application to the Total Syntheses of Alkaloids

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• 作者：Sophie Lauzon ; Franç ; ois Tremblay ; David Gagnon ; Cé ; drickx Godbout ; Christine Chabot ; Catherine Mercier-Shanks ; Sté ; phane Perreault ; Hé ; lè ; ne DeSè ; ve ; Claude Spino
• 刊名：Journal of Organic Chemistry
• 出版年：2008
• 出版时间：August 15, 2008
• 年：2008
• 卷：73
• 期：16
• 页码：6239-6250
• 全文大小：443K
• 年卷期：v.73,no.16(August 15, 2008)
• ISSN：1520-6904

文摘

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.