87895-13-4Relevant articles and documents
Competing and Cycloaddition in the Reactions of Nucleophilic Olefins with Ethyl 3-(Toluene-p-sulphonylazo)but-2-enoate
Clarke, Simon J.,Davies, David E.,Gilchrist, Thomas L.
, p. 1803 - 1807 (2007/10/02)
The title azo-olefin (4) has been isolated as an unstable oil and its cycloaddition reactions with several enol ethers, an enamine, and two alkyl-substituted indoles have been studied.With ethyl vinyl ether the product is the tetrahydropyridazine (5) but with 2-methoxypropene the product is a pyrrole derivative, (7a).Reaction with α-methoxystyrene similarly gives the pyrrole (7b). 2,3-Dihydrofuran adds to give a tetrahydropyridazine, (8), whereas the product from 4,5-dihydro-2-methylfuran is formulated as a dihydropyrrole, (10). 2-Methyl-1-pyrrolidin-1-ylpropene and 1,3-dimethylindole give mixtures of products arising from both and cycloaddition, with N-methyltetrahydrocarbazole, only the product (13) of cycloaddition is detected.The cycloaddition to ethyl vinyl ether is not accelerated in a more polar solvent, but the addition to 2-methoxypropene is 9.5 times faster in acetonitrile than in tetrachloromethane at 298 K.These reactions are interpreted as involving (i) concerted cycloadditions which are subject to retardation by substituents on the nucleophilic olefins, and (ii) additions through highly unsymmetrical transition states.