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Preparation and transmetallation of a triphenylstannyl beta-D-glucopyranoside : a highly stereoselective route to beta-D-C-Glycosides via glycosyl dianions

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1994

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Frey, Oliver
Hoffmann, Matthias
Kessler, Horst
Uhlmann, Peter
Vasella, Andrea

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Helvetica Chimica Acta. 1994, 77(7), pp. 2060-2069. ISSN 0018-019X. eISSN 1522-2675. Available under: doi: 10.1002/hlca.19940770730

Zusammenfassung

The triphenylstannyl β-u-glucopyranoside 4 was synthesized in one step from the 1.2-anhydro-a-uglucopyranose 3 with (hiphenylstannyl)lithium (Scheme 1). Transmetallation of 4 with excess BuLi, followed by quenching the dianion 7 with CD,OD gave (1s)- 1,5-anhydro-3,4,6-tri-O-benzyl-1f -²H]-u-glucitol (8) in 81%
yield (Scheme 2). Trapping of 7 with benzaldehyde, isobutyraldehyde, or acroleine gave the expected β-Dconfigurated products 11,12, and 13 in good yields. Preparation of C-acyl glycosides from acid chlorides, such as acetyl or benzoyl chloride was not practicable, but addition of benzonitrile to 7 yielded 84% of the benzoylated product 14. Treatment of 7 with Me1 led to 15 (30%) along with 40% of 18, C-alkylation being accompanied by halogen-metal exchange. Prior addition of lithium 2-thienylcyanocuprate increased the yield of 15 to 50% and using dimethyl sulfate instead of Me1 led to 77% of 15. No α-D-anomers could be detected, except with ally1 bromide as the electrophile, which yielded in a 1:l mixture of the anomers 16 and 17.

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ISO 690FREY, Oliver, Matthias HOFFMANN, Valentin WITTMANN, Horst KESSLER, Peter UHLMANN, Andrea VASELLA, 1994. Preparation and transmetallation of a triphenylstannyl beta-D-glucopyranoside : a highly stereoselective route to beta-D-C-Glycosides via glycosyl dianions. In: Helvetica Chimica Acta. 1994, 77(7), pp. 2060-2069. ISSN 0018-019X. eISSN 1522-2675. Available under: doi: 10.1002/hlca.19940770730
BibTex
@article{Frey1994Prepa-9646,
  year={1994},
  doi={10.1002/hlca.19940770730},
  title={Preparation and transmetallation of a triphenylstannyl beta-D-glucopyranoside : a highly stereoselective route to beta-D-C-Glycosides via glycosyl dianions},
  number={7},
  volume={77},
  issn={0018-019X},
  journal={Helvetica Chimica Acta},
  pages={2060--2069},
  author={Frey, Oliver and Hoffmann, Matthias and Wittmann, Valentin and Kessler, Horst and Uhlmann, Peter and Vasella, Andrea}
}
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