Synthesis of 1,2,3-triazole derivatives of chloraloses

In this thesis, new bioorthogonal products were synthesized from carbohydrate molecules by using non-cuprous click chemistry. Firstly, α-chloralose (1) containing β-chloralose (2) in rate of 15% as a form of both isomers was crystalized from hot water to get its pure form. Purified α-chloralose (1), β-chloralose (2) and galactocloralose (3), obtained by the reaction of galactose with freshly prepared chloral, derivatives were treated with tosylchloride in order to get tosylated products such as 6-O-tosyl-1,2-O-(R)-trichloroethylidene-α-D-glucofuranose (4), 6-O-tosyl-1,2-O-(S)-trichloroethylidene-α-D-glucofuranose (7) and 6-O-tosyl-1,2-O-(S)-trichloroethylidene-α-D-galactofuranose (10), respectively. In this way, hydroxyl groups at 6 position of monosaccaharide units can easily be tosylated. Then, the azido products, 6-azido-6-deoxy-1,2-O-(R)-tricloroethlylidene-α-D-glucofuranose (5), 6-azido-6-deoxy-1,2-O-(S)-trichloroethylidene-α-D-glucofuranose (8), 6-azido-6-deoxy-1,2-O-(S)-tricloroethylidene-α-D-galactofuranose (11), were obtained by the reactions of these intermediate tosyl derivatives with sodium azide. Afterwards, these azido sugar derivatives (5, 8 and 11) were reacted with dimetilacetylenedicarboxylate to synthesize the 6-[4,5-di-(methoxycarbonyl)- 1,2,3-triazol]-6-deoxy-1,2-O-(R)-tricloroethylidene-α-D-glucofuranose (6), 6-[4,5-di-(methoxycarbonyl)-1,2,3-triazol]-6-deoxy-1,2-O-(S)-tricloroethylidene-α-D-glucofuranose (9) and 6-[4,5-di-(methoxycarbonyl)-1,2,3-triazol]-6-deoxy-1,2-O-(S)-tricloroethylidene-α-D-galactofuranose (12), respectively. Finally, on condition of keeping these new molecules in form of skeleton form available both in carbohydrate unit and 1,2,3 triazole group, synthesis of bioorthogonal derivatives having original structure was realized. Molecular structures of these all final compounds were identified by using FT-IR, 1H-NMR and 13C-NMR spectroscopic techniques and also elemental analysis, melting point analysis and optical rotation measurements were carried out.