Alternative tandem cyclisation pathways in the reaction between imines and enones

Girling, P Ricardo; Batsanov, Andrei S.; Calow, Adam D.J.; Shen, Hong C.; Whiting, Andrew

Alternative tandem cyclisation pathways in the reaction between imines and enones

2016

Girling, P Ricardo | Batsanov, Andrei S. | Calow, Adam D.J. | Shen, Hong C. | Whiting, Andrew

Dihydroisoquinoline reacts with Danishefsky's diene under Lewis acidic conditions or neat, to give low to moderate yields of the formal aza-Diels–Alder, [4+2]-cycloadduct. However, using methoxyvinyl methylketone with Lewis acid catalysis does not give the aza-Diels–Alder adduct, rather a formal [2+2+2]-cycloaddition occurs to provide access to a diacetyl dihydropyridine. Increased Lewis acid loading results in reduced dihydropyridine formation, and instead, a trimerisation reaction of the methoxyvinyl methyl ketone occurs, to give 1,3,5-triacetylbenzene from a different formal [2+2+2]-cycloaddition. The formal [4+2]-cycloaddition reaction of methoxyvinyl methylketone requires a cyclic imine in order to form the dihydropyridine because the reaction with acyclic imines produced a dihydropyridine from a formal [1+2+1+2]-cycloaddition. Evidence resulting from the isolation of reaction intermediates and in situ spectroscopic studies, shows that the reaction between 3,4-dihydroisoquinoline and methyl vinyl ketone, catalysed by oxy-philic Lewis acids, proceeds via a Mannich-Michael pathway and an imminium ion species. All reactions occur by one-pot cascade routes.

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