Abstract
The [3,3]-sigmatropic allyl cyanate/isocyanate rearrangement of glycals in the presence of O-, N-, and C-nucleophiles afforded β-N-glucosyl and galactosyl carbamates, ureas, and amides in good yields. The unsaturated products were elaborated to N-glycosides by dihydroxylation, to 1,3-diaminosugars by tethered aminohydroxylation, or to 1,2-diaminosugars by iteration of the sigmatropic rearrangement. This metal-free methodology represents an excellent and general method for the stereoselective synthesis of N-glycosides and diamino sugars with complete transmission of stereochemical information.
Highlights
The [3,3]-sigmatropic allyl cyanate/isocyanate rearrangement of glycals in the presence of O, N, and C-nucleophiles afforded β-Nglucosyl and galactosyl carbamates, ureas, and amides in good yields
N-Glycosides (1-aminosugars and derivatives)[2] are a subclass which may serve as synthetic intermediates, besides playing a key role in N-linked glycoproteins involved in many recognition events or in nucleosides and antibiotics.2b Representative examples (Figure 1) include the N-acetyl-D-glucosamine asparagine moiety 1, a key agent in cell-recognition and signal transduction,[3] glycocinnamoylspermidines 2, broad spectrum antibacterial agents,[4] staurosporine 3, displaying anticancer activity,[5] and trehazoline 4, a potent and specific inhibitor of trehalase.[6]
Known Procedures for the Synthesis of NGlycosides from Glycals and the Strategy Reported Based on the Allyl Cyanate/Isocyanate Rearrangement versatility of the resulting isocyanates
Summary
The [3,3]-sigmatropic allyl cyanate/isocyanate rearrangement of glycals in the presence of O-, N-, and C-nucleophiles afforded β-Nglucosyl and galactosyl carbamates, ureas, and amides in good yields. We report our results on the application of the allyl cyanate/isocyanate rearrangement to glycals to give Nglycosides (Scheme 1, route d) and diaminosugar derivatives.
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