Solvent-Dependent Mechanism and Stereochemistry of Mitsunobu Glycosylation with Unprotected Pyranoses
- Hironori TakeuchiHironori TakeuchiInstitute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, JapanMore by Hironori Takeuchi,
- Yusuke FujimoriYusuke FujimoriInstitute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, JapanMore by Yusuke Fujimori,
- Yoshihiro UedaYoshihiro UedaInstitute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, JapanMore by Yoshihiro Ueda,
- Hiromitsu ShibayamaHiromitsu ShibayamaInstitute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, JapanMore by Hiromitsu Shibayama,
- Masaru NagaishiMasaru NagaishiInstitute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, JapanMore by Masaru Nagaishi,
- Tomoyuki YoshimuraTomoyuki YoshimuraInstitute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, JapanMore by Tomoyuki Yoshimura,
- Takahiro SasamoriTakahiro SasamoriInstitute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, JapanMore by Takahiro Sasamori,
- Norihiro TokitohNorihiro TokitohInstitute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, JapanMore by Norihiro Tokitoh,
- Takumi FurutaTakumi FurutaInstitute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, JapanMore by Takumi Furuta, and
- Takeo Kawabata*Takeo Kawabata*Email: [email protected]Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, JapanMore by Takeo Kawabata
Abstract
An SN2 mechanism was proposed for highly stereoselective glycosylation of benzoic acid with unprotected α-d-glucose under Mitsunobu conditions in dioxane, while an SN1 mechanism was indicated for nonstereoselective glycosylation in DMF. The SN2-type stereoselective Mitsunobu glycosylation is generally applicable to various unprotected pyranoses as glycosyl donors in combination with a wide range of acidic glycosyl acceptors such as carboxylic acids, phenols, and imides, retaining its high stereoselectivity (33 examples). Glycosylation of a carboxylic acid with unprotected α-d-mannose proceeded also in an SN2 manner to directly afford a usually less accessible 1,2-cis-mannoside. One- or two-step total syntheses of five simple natural glycosides were performed using the glycosylation strategy presented here using unprotected α-d-glucose.
Cited By
This article is cited by 3 publications.
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- Xin Qiu, Antony J. Fairbanks. Scope of the DMC mediated glycosylation of unprotected sugars with phenols in aqueous solution. Organic & Biomolecular Chemistry 2020, 18 (37) , 7355-7365. https://doi.org/10.1039/D0OB01727B