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Stereodivergent Synthesis of Piperidine Alkaloids by Ring‐Rearrangement Metathesis/Reductive Lactam Alkylation of Nitroso Diels–Alder Cycloadducts
Author(s) -
Vincent Guillaume,
Karila Delphine,
Khalil Georges,
Sancibrao Pierre,
Gori Didier,
Kouklovsky Cyrille
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201300836
Subject(s) - piperidine , cyclopentadiene , chemistry , lactam , metathesis , nitroso , bicyclic molecule , diels–alder reaction , alkylation , stereochemistry , ring (chemistry) , medicinal chemistry , organic chemistry , catalysis , polymer , polymerization
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.