Efficient Access to Aminomannoside Derivatives via Formal [2+2] Cycloaddition of Triazolinediones and Tri-O-acetyl-d-glucal

Abstract

Triazolinediones react with tri-O-acetyl-d-glucal to provide the corresponding diazetidines as single stereoisomers possessing the mannosamine configuration at C2. The diazetidines undergo facile ring opening with alcohol and amine nucleophiles. While this methodology is not fully developed, it is the first example of direct intermolecular conversion of a glycal to a mannosamine derivative. Computational analysis provides mechanistic insight that in turn leads to a proposal for the generation of glucosamine derivatives from glycals and triazolinediones.

Key words

aminoglycoside - cycloaddition - diastereoselectivity - glycal - mechanism

References

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Computational studies of the ene reaction of triazolinedione and tetramethylbutene suggest that there is a central biradical intermediate connecting the starting materials, the aziridine imine and the ene product. For discussion, see ref. 11b.

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