title: Stereodivergent synthesis of piperidine alkaloids by ring-rearrangement metathesis/reductive lactam alkylation of nitroso Diels-Alder cycloadducts.
abstract: A general methodology for the stereoselective synthesis of 2-(2-hydroxyalkyl)piperidine alkaloids by ring-rearrangement metathesis of nitroso Diels-Alder cycloadducts is reported. The approach is illustrated by the formal synthesis of porantheridine and the total synthesis of andrachcinidine through a diastereodivergent allylation of an N-alkoxy bicyclic lactam. The asymmetric synthesis of the latter alkaloid provides new insights into the configurational stability of cycloadducts between chloronitroso reagents and cyclopentadiene.
authors.affiliation: Institut de Chimie Moléculaire et des Matériaux d'Orsay (UMR 8182), Univ. Paris-Sud, 91405 Orsay, France. guillaume.vincent@u-psud.fr
authors.forename: Guillaume
authors.initials: G
authors.lastname: Vincent
authors.forename: Delphine
authors.initials: D
authors.lastname: Karila
authors.forename: Georges
authors.initials: G
authors.lastname: Khalil
authors.forename: Pierre
authors.initials: P
authors.lastname: Sancibrao
authors.forename: Didier
authors.initials: D
authors.lastname: Gori
authors.forename: Cyrille
authors.initials: C
authors.lastname: Kouklovsky
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis*; D000478:Alkylation; D007769:Lactams / Q000737:chemistry*; D015394:Molecular Structure; D010880:Piperidines / Q000138:chemical synthesis*; D013237:Stereoisomerism
chemical_list: D000470:Alkaloids; D007769:Lactams; D010880:Piperidines; C585228:andrachcinidine; C450779:porantheridine
keywords: alkaloids; asymmetric synthesis; lactams; metathesis; piperidines