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. 2020 Nov 20;22(22):9041-9046.
doi: 10.1021/acs.orglett.0c03438. Epub 2020 Nov 4.

Allyl Cyanate/Isocyanate Rearrangement in Glycals: Stereoselective Synthesis of 1-Amino and Diamino Sugar Derivatives

Stefania Mirabella  1 , Giulia Petrucci  1 , Cristina Faggi  1 , Camilla Matassini  1 , Francesca Cardona  1 , Andrea Goti  1
Affiliations

Allyl Cyanate/Isocyanate Rearrangement in Glycals: Stereoselective Synthesis of 1-Amino and Diamino Sugar Derivatives

Stefania Mirabella et al. Org Lett. .

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.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Examples of natural N-glycosides.
Scheme 1
Scheme 1. Known Procedures for the Synthesis of N-Glycosides from Glycals and the Strategy Reported Herein Based on the Allyl Cyanate/Isocyanate Rearrangement
Scheme 2
Scheme 2. Synthesis of the d-Glucal Carbamate 6a and the d-Galactal Carbamate 6b and the Expected Rearrangement to Yield the N-Glycosides 9
Scheme 3
Scheme 3. TS Involved in the Rearrangement
Scheme 4
Scheme 4. Synthesis of N-Guloside 21 by cis-Dihydroxylation of Hexenopyranoside 11b and of 1,3-Diaminoallose 25 by Tethered Aminohydroxylation of Hexenopyranoside 24
Scheme 5
Scheme 5. Iterative Allyl Cyanate/Isocyanate Rearrangement to Yield the 1,2-Diamino Sugar 27
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