Denitrogenative rearrangement reaction

Triazoles also serve as a precursor of metal carbene complexes. For instance, Murakami and Fokin independently reported a denitrogenative rearrangement reaction of triazolyl alcohol 69 (Scheme 7.27) [41]. The ring-chain tautomeriza-tion of 69 generates its diazo imine form, which reacts with Rh2(Oct)4 to produce a rhodium carbene complex. The following 1,2-alkyl migration and elimination of rhodium produce enaminone 70. 

Photoisomerization of c/.y-stilbene 191 Ionic fragmentation reaction 191 Cyclopropyl radical ring-opening 192 Ionic molecular rearrangement 193 Ene reaction 196 Thermal denitrogenation 198 Unimolecular dissociation 199 Sn2 reaction 200... 

Triazoles could be converted to other structures. Rhodium-catalyzed denitrogenative [2,3]-sigmatropic rearrangements of 1,2,3-triazoles 108 with allyl sulfides 109 afforded imines 110 (13CEJ15115). Reactions of benzotriazoles with 1,3-diketones in the presence of potassium terf-butox-ide under N-bromosuccinimide conditions provided mixtures of AT-l and N-2 alkylation products (13TL295). 

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