Abstract
Possible cyclization pathways for the reaction of (1E,2E)-N-(but-2-en-1-ylidene)triflamide with N,N'-dimethylcarbodiimide have been investigated by DFT and MP2 calculations. The [4+2] route is shown to be thermodynamically unfavorable due to a small content of the reactive s-cis conformer of the azadiene. The [2CN+2CN] route has ΔGº>0 and therefore is thermodynamically forbidden. The only allowed route is the [2CN+2CC] cycloaddition, which has ΔGº < 0 and leads to 2-methylimino-3-(2-trifliminomethyl)-1,4-dimethylazetidine with further isomerization to 3-(triflamidomethylidene)-2-methylimino-1,4-dimethylazetidine in full agreement with the experimental results. These results indicate the necessity of considering free energy changes rather than only enthalpy changes for accurate prediction of the course of cyclization reactions.
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