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Asymmetric Synthesis of (−)-Anatoxin-a via an Asymmetric Cyclization Using a New Ligand for Pd-Catalyzed Alkylations

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Barry M. Trost* and Johan D. Oslob

Contribution from the Department of Chemistry, Stanford University, Stanford, California 94305-5080

J. Am. Chem. Soc., 1999, 121 (13), pp 3057–3064

DOI: 10.1021/ja983617d

Publication Date (Web): March 19, 1999

Section:

Alkaloids

Abstract

Palladium-catalyzed asymmetric allylic alkylations have been explored in the context of medium-sized ring substrates, intramolecular vs intermolecular processes involving attack on a formally meso π-allyl intermediate in the desymmetrization, and the presence of electron-withdrawing groups on the cationic π-allylpalladium intermediate. The synthesis of anatoxin-a, also known as the “very fast death factor”, raises all of these questions. Ligands derived from trans-1,2-diaminocyclohexane and 2-diphenylphosphinobenzoic acid effect asymmetric alkylations with an allyl substrate bearing an electron-withdrawing group. On the other hand, a new type of ligand wherein the diamine is derivatized with both 2-diphenylphosphinobenzoic acid and 2-picolinic acid was required to effect asymmetric cyclization to form the 9-azabicyclo[4.2.1]non-2-ene system. A total synthesis of anatoxin-a from 5-hydroxy-1,8-nonadiene employing a metathesis reaction to form the cycloheptene and a palladium-catalyzed asymmetric cyclization to form the bicyclic ring system is achieved in 15% overall yield.

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