An efficient synthesis of the polar part of sulfamisterin and its analogs

An efficient synthesis of the polar part of sulfamisterin and its analogs starting from d-xylose is described. The corresponding allylic thiocyanates and trichloroacetimidates were subjected to aza-Claisen rearrangement that effectively generated a quaternary carbon having an amino group as one of the substituents. Subsequent functional group interconversions afforded the highly functionalized branched aminopolyol 29 that is expected to have the crucial application in the construction of sulfamisterin. On the other hand, the second diastereoisomer 34 would be transformed to 2-epi-congener. With respect to the appropriate stereochemical arrangement, the prepared polar segments 29 and 34 can also be utilized for the synthesis of mycestericins (E, G) and their analogs.

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► Aza-Claisen rearrangement as the key transformation.
► The observed selectivity was supported by DFT calculations.
► Rearrangements were accelerated using microwave irradiation.
► Hydroxylated oxazolidinones represent the polar part of sulfamisterin.