The azaphilic addition of organometallic reagents on tetrazines: scope and limitations

Environmentally compatible next generation green energetic materials (GEMs)

“…Recently, there has been considerable attention has been paid in the study of [14][15][16][17][18] tetrazine compounds. Tetrazine moiety displayed unique and interesting characteristic properties and has been utilized for the preparation of several energetic materials [19].…”

Unusual Expansion of the 1,2,4,5‐Tetrazine Ring in [1,2,4]Triazolo[4,3‐b][1,2,4,5]tetrazines Leading to [1,2,4,6]Tetrazepine Systems

“…Although nucleophilic attack at a nitrogen atom is not typical for the vast majority of heterocyclic compounds, there are some examples in tetrazine chemistry where the extremely electron-deficient tetrazine ring undergoes azaphilic additions with methyllithium, Grignard reagents, or organozinc compounds to give 1-alkyl-or 1-aryl-substituted 1,4-dihydrotetrazines. [12,13] These literature data can be considered as an argument in favor of the first step of the suggested mechanism. Moreover, according to quantum chemical calculations the LUMO distribution in triazolotetrazines has the maximal coefficient for the N-8 nitrogen, [16] thus indicating that this nitrogen atom appears to be the most plausible site for nucleophilic attack.…”

“…[1][2][3][4][5][6][7] Also, some carbon modifications of 1,2,4,5-tetrazines due to displacement reactions with anhydro bases of quinaldinium salts [8] and heterocyclic carbenes [9] or by cross-coupling reactions with arylboronic acids [10] and acetylenes [11] have been reported. There are also examples where instead of nucleophilic substitution reactions at C-3 or C-6, azaphilic addition [12,13] or [4+2]cycloaddition reactions [8,14] have been observed to give rise to the corresponding 1,4-dihydrotetrazines or pyridazine derivatives, respectively.…”

Unusual Investigation of Polycyclic Saturated Tetrazine: A Breakthrough to 1,2,4,5‐Tetrazine

“…In order to continue efforts in this field [25][26][27][28][29], the author now report on the spectral predication of polycyclic saturated tetrazine compound. All studies have been done in this investigation by focusing on the readily available 1,2,4,5-tetrazine as starting materials as per the literature procedures [30][31][32][33][34].…”