Betaine-carbene interconversions. From N-ylides to zwitterionic N-heterocyclic carbene-borane adducts.

In the presence of NBS 3-methylindole reacted with various imidazoles to give the (indol-2-yl)imidazolium salts 21a–f, which were converted in aqueous solution into the 2-(imidazolium-3-yl)-3-methylindolates 22a–f by base. These conjugated ylides—which represent a subclass of mesomeric betaines—are the exclusively detectable form in the NMR spectra taken in DMSO-d6. A DFT calculation revealed that the betaine 22a is −9.3 kJ/mol more stable than the tautomeric N-heterocyclic carbene 23a and that the energy for the betaine–carbene interconversion is ΔG⧧ = 66.4 kJ/mol. The N-heterocyclic carbenes (3-methyl-indol-2-yl)imidazol-2-ylidenes, however, can be trapped by sulfur, triethylborane, and triphenylborane. Whereas the first trapping reaction yielded the expected imidazolethiones, the borates gave the first representatives of new zwitterionic borane adducts, imidazo[2′,1′:3,4][1,4,2]diazaborolo[1,5-a]indolium-11-ides 26a–h. We performed DFT calculations on the structures of mesomeric betaine 22a, the carben...