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Review | Regular issue | Vol 78, No. 2, 2009, pp.281-318
Published online, 2nd October, 2008
DOI: 10.3987/REV-08-641
Synthesis of Nitrogen Heterocycles Utilizing Molecular Nitrogen as a Nitrogen Source and Attempt to Use Air Instead of Nitrogen Gas

Miwako Mori*

*Health Sciences University of Hokkaido, Ishikari-Tobetsu 061-0293, Japan

Abstract

Nitrogen fixation using transition metals is a challenging subject. Using a titanium-nitrogen complex, discovered by Yamamoto in 1967, and titanium isocyanate complex, molecular nitrogen could be incorporated into organic compounds to afford various heterocyclic compounds. Furthermore, novel titanium-catalyzed nitrogenation procedure was developed. That is, a THF solution of TiCl4 or Ti(OiPr)4, and an excess amount of Li and TMSCl was stirred under nitrogen (1 atm) at room temperature overnight and to this solution was added phthalic anhydride. The whole solution was refluxed overnight to afford a phthalimide in over 100 % yield. Using the stoichiometric conditions of the novel nitrogenation, various indole, pyrrole, pyrrolizine, indolizine derivatives and lactams were obtained in good to moderate yields after usual workup. Although the structure of the titanium-nitrogen complex has not been determined yet, the complex is thought to be a mixture of N(TMS)3, TiX2N(TMS)2 and XTi=NTMS. Nitrogen in air could be directly fixed using this method, and the natural products, such as monomoline I, lycopodine and pumiliotoxin C, could be synthesized from nitrogen in air as a nitrogen source.