Fenoksi-koordine iridyum(III) N-heterosiklik karben komplekslerinin sentezi ve indirgen aminasyon tepkimelerindeki katalitik aktivitelerinin incelenmesi

Amines are highly valuable compounds used in, chemical synthesis, fine chemicals, pharmaceuticals, and agrochemicals. Although they are widely available in nature, those mentioned fields create a need for synthetic amine derivatives. Among the methods of amine synthesis, the most widely used method is the reduction of imines. But this important method contains some restrictions; one of the great difficulties is the synthesis of imines due to their limited stability (for example, they are sensitive to moisture and air.). Nowadays, one of the effective alternative methods for resolving this problem is reductive amination (RA) reactions; in which amines, could be catalytically synthesized. (Kobayashi and Ishitani, 1999; Gomez et. al, 2002; Breuer et. al, 2004; Abdel-Magid and Mehrman, 2006; Guillena et. al, 2010). The principal aim of this thesis research was to prepare a series of phenoxide-coordinated iridium(III) N-heterocyclic carbene complexes and investigate their catalytic activities in transfer reductive amination reactions. For this purpose, seven phenoxide- or napthoxide-coordinated iridium(III) N-heterocyclic carbene complex were synthesized and fully characterized. Then, the catalytic activities of the corresponding complexes were investigated in the RA reactions of various ketones and aldehydes with amines. It has been observed that these complexes catalyze RA reactions effectively, within the complexes tested, the naphthoxy-coordinated complex with the imidazole ring has the best activity. Catalytic experiments were carried out over a wide range of substrates and reached TON values up to 490 in ketones and 14800 in aldehydes. Keywords: N-heterocyclic carbene, Phenoxide-coordinated iridium(III) NHC complexes, Transfer hydrogenation, Reductive amination. 1.Abdel-Magid, A. F.; Mehrman, S. 2006, J. Org. Process Res. Dev., 10, 971−1031. 2.Breuer, M.; Ditrich, K.; Habicher, T.; Hauer, B.; Keßeler, M.; Stürmer, R.; Zelinski, T. 2004, Angew. Chem., Int. Ed., 43, 788−824. 3.Gomez, S.; Peters, J. A.; Maschmeyer, T. 2002, Adv. Synth. Catal., 344, 1037−1057. 4.Guillena, G.; Ramon, D. J.; Yus, M. 2010, Chem. Rev., 110, 1611−1641. 5.Gülcemal, D.; Gülcemal, S.; Robertson, C. M.; Xiao, J. 2015, Organometallics, 34, 4394-4400. 6.Kobayashi, S.; Ishitani, H. 1999, Chem. Rev., 99, 1069−1094.