Synthesis of heterocycles from molecular nitrogen as a nitrogen source

Nitrogen fixation is a very attractive process. We succeeded in nitrogen fixation using a TiCl4‐ or Ti(O‐i‐Pr)4‐Li‐TMSCl system. Nitrogen fixation proceeds at room temperature under 1 atmosphere pressure of nitrogen to give a mixture of titanium nitride complex 12, titanium nitrogen complex 13, and N(TMS)4. Using the titanium nitrogen complexes 1, various heterocycles were synthesized from the corresponding ketocarbonyl compounds. Nitrogen in air could be fixed using this method. The total syntheses of lycopodine and monomolin I were achieved from nitrogen in air as the nitrogen source. On the other hand, transmetalation of the nitrogen moiety of titanium nitrogen complexes 1 to a palladium complex was realized, and the non‐substituted anilines could be synthesized from ArX and N2 in the presence of the palladium catalyst. Furthermore, amide could be synthesized from ArX, CO, and N2 using the palladium catalyst.