Glycals (1) and exo-glycals (2) are widely used substrates in the synthesis of carbohydrate derivatives and natural products [1-4]. The reactivity of these compounds is characterized by electrophilic ionic and radical additions to the electron rich double bond. The goal of our research was to study the haloamination of exo- and endo-glycals, as the products of these reactions - the vicinal haloamine derivatives (3 - 5) - can be transformed into synthetically valuable intermediates by nucleophilic substitution or spirocyclization .
The haloamination reaction of alkenes has been described several times before , but in case of endo-glycals only a few examples are known, and the reactions of exo-glycals have not been studied yet. Using exo- and endo-glycals as starting materials, the effects of the configuration of carbohydrate skeleton, protecting groups and substituents on the yield and selectivity have been examined.
The research was supported by the EU and co-financed by the European Regional Development Fund under the project GINOP-2.3.2-15-2016-00008, and by the National Research, Development and Innovation Office under the project FK128766.
- Fürstner, A.; Weidmann, H. J. Carbohydr. Chem. 1988, 7(4), 773-783.
- Danishefsky, S. J.; Bilodeau, M. T. Angew. Chem. Int. Ed. Engl. 1996, 35, 1380-1419.
- Chen H.; Xian, T.; Zhang, W.; Si, W.; Luo, X.; Zhang, B.; Zhang, M.; Wang, Z.; Zhang, J. Carbohydr. Res. 2016, 431, 42-46.
- Priebe, W.; Fokt, I.; Grynkiewicz, G., Glycal Derivatives. In Glycoscience: Chemistry and Chemical Biology, Fraser-Reid, B.; Tatsuta, K.; Thiem, J., Eds. Springer: Berlin, Heidelberg, 2008, pp 699 - 735
- Gandhi, S.; Bisai, A.; Prasad, B. A. B.; Singh, V. K.; J. Org. Chem. 2007, 72, 2133-2142
- Dauban, P.; Darses, B.; Jarvis, A.; Addition Reactions with Formation of Carbon-Nitrogen Bonds In Comprehensive Organic Synthesis II. (Second Edition), P. Knochel, G. A. Molander Ed., Elsevier; Ltd. 2014; p 586-592.