Premium
Ring‐Rearrangement Metathesis of Nitroso Diels–Alder Cycloadducts
Author(s) -
Vincent Guillaume,
Kouklovsky Cyrille
Publication year - 2011
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.201002558
Subject(s) - alkene , metathesis , chemistry , ruthenium , nitroso , grubbs' catalyst , salt metathesis reaction , ring (chemistry) , double bond , epimer , diels–alder reaction , adduct , ring closing metathesis , photochemistry , stereochemistry , catalysis , medicinal chemistry , organic chemistry , polymerization , polymer
Strained nitroso Diels–Alder bicyclo[2.2.1] or [2.2.2] adducts functionalized with alkene side chains of diverse length undergo a ring‐rearrangement metathesis process with external alkenes and Grubbs II or Hoveyda–Grubbs II ruthenium catalysts, under microwave irradiation or classical heating, to deliver cis ‐fused bicycles of various ring sizes, which contain a NO bond. These scaffolds are of synthetic relevance for the generation of molecular diversity and to the total synthesis of alkaloids. The observation of unexpected reactions, such as epimerization or one‐carbon homologation of the alkene side chain, is also reported.