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. 2020 Jul 17;22(14):5622-5626.
doi: 10.1021/acs.orglett.0c01986. Epub 2020 Jul 7.

Stereoselective Protection-Free Modification of 3-Keto-saccharides

Nittert Marinus  1 , Nabil Tahiri  1 , Margherita Duca  1 , L M C Marc Mouthaan  1 , Simona Bianca  1 , Marco van den Noort  2 , Bert Poolman  2 , Martin D Witte  1 , Adriaan J Minnaard  1
Affiliations

Stereoselective Protection-Free Modification of 3-Keto-saccharides

Nittert Marinus et al. Org Lett. .

Abstract

Unprotected 3-keto-saccharides have become readily accessible via site-selective oxidation, but their protection-free functionalization is relatively unexplored. Here we show that protecting groups are obsolete in a variety of stereoselective modifications of our model substrate methyl α-glucopyranoside. This allows the preparation of rare sugars and the installation of click handles and reactive groups. To showcase the applicability of the methodology, maltoheptaose has been converted into a chemical probe, and the rare sugar evalose has been synthesized.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Reported face-selective additions to a keto-saccharide.
Scheme 1
Scheme 1. Overview of Previous and Herein Reported Work
Scheme 2
Scheme 2. Grignard Reaction, Indium-Mediated Alkylations, and Nitroaldol Reaction
Scheme 3
Scheme 3. Epoxidation of 1 with Diazomethane and Further Modification of 7
Scheme 4
Scheme 4. Oxidation of β-d-Maltoheptoasyl Azide and Subsequent Epoxide Formation
Scheme 5
Scheme 5. Synthesis of Kanosamine and Cyanohydrin Formation
Scheme 6
Scheme 6. Methylenation and Further Modifications
Scheme 7
Scheme 7. Synthesis of Methyl α-d-Evalose
See this image and copyright information in PMC

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