Doubly Coarctate-Stabilized
Carbenes: Synthetic and
Computational Studies
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Abstract
Isoindazoles joined by an ethynyl linker to either a
phenyltriazene
or a phenyldiazene moiety were synthesized, and their subsequent reactivity
was examined. Computations suggest that these molecules could rearrange
at moderate temperatures via carbene intermediates that are doubly
stabilized by coarctate conjugation. The experimental results corroborate
the calculations, as the transient carbene can either be trapped with
oxygen or undergo ring-opening to afford a rearranged product. Additional
calculations illustrate some design principles that might lead to
stable carbenes that are the global minimum on the coarctate hypersurface