Synthesis of a Dihydropyranonucleoside Using an Oxidative Glycosylation Reaction­ Mediated by Hypervalent Iodine

Hiroya Kan-no; Yukako Saito; Shun Omoto; Sakie Minato; Hideaki Wakamatsu; Yoshihiro Natori; Tomozumi Imamichi; Hiroki Takahata; Yuichi Yoshimura

doi:10.1055/s-0033-1340663

Synthesis, Table of Contents

Synthesis 2014; 46(07): 879-886
DOI: 10.1055/s-0033-1340663

paper

Synthesis of a Dihydropyranonucleoside Using an Oxidative Glycosylation Reaction Mediated by Hypervalent Iodine

Authors

Hiroya Kan-no

^aFaculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan Fax: +81(22)2752013 Email: yoshimura@tohoku-pharm.ac.jp
Yukako Saito

^aFaculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan Fax: +81(22)2752013 Email: yoshimura@tohoku-pharm.ac.jp
Shun Omoto

^aFaculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan Fax: +81(22)2752013 Email: yoshimura@tohoku-pharm.ac.jp
Sakie Minato

^aFaculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan Fax: +81(22)2752013 Email: yoshimura@tohoku-pharm.ac.jp
Hideaki Wakamatsu

^aFaculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan Fax: +81(22)2752013 Email: yoshimura@tohoku-pharm.ac.jp
Yoshihiro Natori

^aFaculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan Fax: +81(22)2752013 Email: yoshimura@tohoku-pharm.ac.jp
Tomozumi Imamichi

^bLeidos Biomedical Research, Inc., Frederick National Laboratory for Cancer Research, Frederick, MD 21702, USA
Hiroki Takahata*

^aFaculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan Fax: +81(22)2752013 Email: yoshimura@tohoku-pharm.ac.jp
Yuichi Yoshimura*

^aFaculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan Fax: +81(22)2752013 Email: yoshimura@tohoku-pharm.ac.jp

Abstract

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Abstract

As a part of our ongoing studies of structure–activity relationships regarding cyclohexenyl nucleosides, we were prompted to synthesize a dihydropyranonucleoside as a potential anti-HIV agent. The synthesis of a glycal moiety started from but-2-enediol, which was converted into a di-PMB derivative in several steps. The introduction of an allyl group followed by ring-closing metathesis gave a dihydropyran derivative. After isomerization of the double bond catalyzed by Wilkinson’s catalyst, the resulting glycal, 2,3-bis[(4-methoxybenzyloxy)methyl]-3,4-dihydro-2H-pyran, was subjected to an oxidative glycosylation reaction mediated by hypervalent iodine. Treatment of 2,3-bis[(4-methoxybenzyloxy)methyl]-3,4-dihydro-2H-pyran with (PhSe)₂/PhI(OAc)₂/TMSOTf (cat.) gave the desired pyranyluracils as a mixture of anomers that were converted into the final target, dihydropyranocytidine, after several manipulations and separation of the anomers.

Key words

glycosylation - nucleoside - oxidation - iodine - antiviral

Full Text

References

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Supplementary Material

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Synthesis of a Dihydropyranonucleoside Using an Oxidative Glycosylation Reaction­ Mediated by Hypervalent Iodine

Authors

Synthesis of a Dihydropyranonucleoside Using an Oxidative Glycosylation Reaction Mediated by Hypervalent Iodine