The judicious selection of protecting groups is one of the most important factors for the successful synthesis of complex molecules. In the course of our synthetic studies of natural products, we recently developed 1- and 2-naphthylmethoxymethyls (NAPOMs) as facilely installable and oxidatively removable protecting groups for alcohols. The NAPOMs can be introduced in mild conditions; e.g. NAPOMCl, i-Pr2EtN, various solvents, room temperature (rt) and easily be removed via oxidation using dichlorodicyanobenzoquinone (DDQ) or ceric ammonium nitrate (CAN) in the presence of H2O, or hydrogenolysis. It is worthy to note that the selective removal of the 2-NAPOM in the presence of 2-naphthylmethyl (NAP) is possible via acidic methanolysis, whereas, that in the presence of p-methoxymethyl (PMB) and even 1-NAPOM is enabled via hydrogenolysis using Pd/C. Besides, we also found that the 1-NAPOM group can be removed in the presence of PMB and benzyloxymethyl (BOM) groups. These useful properties of NAPOMs forced us to apply them to the synthesis of natural products, especially to that of glycosides where various protecting groups are examined to induce stereoselective glycosyl bond formations. In this preesentation, we will discuss the detailed properties of 1- and 2-NAPOM groups, as well as our recent application study to the glycoside synthesis, in which these developed protecting groups act as powerful tools to achieve the stereoselective glycosylation. Furthermore, an applicational study to the total synthesis of a natural product may also be introduced.

Development of novel benzyloxymethyl protecting groups and their application to the stereoselective glycosylation

255th National Meeting (2018)

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