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Synlett 2003(9): 1303-1306
DOI: 10.1055/s-2003-40337
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Catalytic Glycosylation with Rhodium(III)-Triphos Catalysts

Beatrice Wagnera, Michael Heneghanb, Gerhard Schnabelc, Beat Ernst*a
a Institute of Molecular Pharmacy, Pharmacenter, University of Basel, Klingelbergstrasse 50, 4056 Basel, Switzerland
e-Mail: beat.ernst@unibas.ch;
b Present address: Ciba Speciality Chemicals, 4002 Basel, Switzerland
c Present address: Bayer CropScience GmbH, Industriepark Hoechst, 65926 Frankfurt, Germany
Further Information

Publication History

Received 27 March 2003
Publication Date:
30 June 2003 (online)

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Abstract

The formation of glycosides in high yield from 1-hydroxy sugars using catalytic amounts (0.5mol%) of Rh(III)Cl3(triphos) (1a) or [Rh(III)(MeCN)3(triphos)](TfO)3 (1b) is described. High stereocontrol at the anomeric center is achieved by neighboring group participation. In addition, an application of this new glycosylation procedure for the synthesis of a derivative of the oviposition-deterring pheromone of the cherry fruit fly Rhagoletis cerasi is presented.

Key words

catalytic glycosylation - Rh(III)triphos catalysts - 1-hydroxy sugars - O-glycosides - oviposition-deterring pheromone

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12

22 was prepared in analogy to 19. [11]

17

13C NMR (CDCl3, 50 MHz) of 26: 25.2(2t), 25.8 (t), 26.0 (t), 29.2 (t), 29.3(2t), 29.4 (t), 29.6 (t), 29.7 (t), 33.8 (t), 55.6 (q), 68.6 (t), 69.0 (t), 69.7 (t), 70.7 (t), 73.5 (t), 73.9 (d), 74.8(2t), 75.3 (d), 78.1 (d), 79.0 (d), 82.8 (d), 101.2 (d), 114.6-132.8 (29d, aromatic CH), 130.2 (s), 137.9 (s), 138.0 (s), 138.2 (s), 139.2 (s), 153.3 (s), 153.7 (s), 165.0 (s).

18

13C NMR (CD3OD, 50 MHz) of 30: 26.9-51.8(14t), 63.1 (t, C-6′), 71.2 (d, C-4′), 72.0 (t, C-15), 72.7 (d, C-8), 75.4 (d, C-2′), 78.1, 78.4 (2d, C-3′, C-5′), 104.6 (t, C-1′), 176.5 (s, C-1).