Use of sultines in the asymmetric synthesis of polypropionate antibiotics
- Vogel, Pierre 1Laboratory of Glycochemistry and Asymmetric Synthesis (LGSA), Swiss Federal Institute of Technology (EPFL), Batochime, CH-1015 Lausanne, Switzerland
- Turks, Maris 1Laboratory of Glycochemistry and Asymmetric Synthesis (LGSA), Swiss Federal Institute of Technology (EPFL), Batochime, CH-1015 Lausanne, Switzerland
- Bouchez, Laure 1Laboratory of Glycochemistry and Asymmetric Synthesis (LGSA), Swiss Federal Institute of Technology (EPFL), Batochime, CH-1015 Lausanne, Switzerland
- Craita, Cotinica 1Laboratory of Glycochemistry and Asymmetric Synthesis (LGSA), Swiss Federal Institute of Technology (EPFL), Batochime, CH-1015 Lausanne, Switzerland
- Murcia, M. Carmen 1Laboratory of Glycochemistry and Asymmetric Synthesis (LGSA), Swiss Federal Institute of Technology (EPFL), Batochime, CH-1015 Lausanne, Switzerland
- Fonquerne, Freddy 1Laboratory of Glycochemistry and Asymmetric Synthesis (LGSA), Swiss Federal Institute of Technology (EPFL), Batochime, CH-1015 Lausanne, Switzerland
- Didier, Charles 1Laboratory of Glycochemistry and Asymmetric Synthesis (LGSA), Swiss Federal Institute of Technology (EPFL), Batochime, CH-1015 Lausanne, Switzerland
- Huang, Xiaogen 1Laboratory of Glycochemistry and Asymmetric Synthesis (LGSA), Swiss Federal Institute of Technology (EPFL), Batochime, CH-1015 Lausanne, Switzerland
- Flowers, Christopher 1Laboratory of Glycochemistry and Asymmetric Synthesis (LGSA), Swiss Federal Institute of Technology (EPFL), Batochime, CH-1015 Lausanne, Switzerland
Published in:
- Pure and Applied Chemistry. - Walter de Gruyter GmbH. - 2008, vol. 80, no. 4, p. 791-805
English
At low temperature and in the presence of an acid catalyst, SO2 adds to 1,3-dienes equilibrating with the corresponding 3,6-dihydro-1,2-oxathiin-2-oxides (sultines). These compounds are unstable above -60 °C and equilibrate with the more stable 2,5-dihydrothiophene 1,1-dioxides (sulfolenes). The hetero-Diels-Alder additions of SO2 are suprafacial and follow the Alder endo rule. The sultines derived from 1-oxy-substituted and 1,3-dioxy-disubstituted 1,3-dienes cannot be observed at -100 °C but are believed to be formed faster than the corresponding sulfolenes. In the presence of acid catalysts, the 6-oxy-substituted sultines equilibrate with zwitterionic species that react with electron-rich alkenes such as enoxysilanes and allylsilanes, generating β,γ-unsaturated silyl sulfinates that can be desilylated and desulfinylated to generate polypropionate fragments containing up to three contiguous stereogenic centers and an (E )-alkene unit. Alternatively, the silyl sulfinates can be reacted with electrophiles to generate polyfunctional sulfones (one-pot, four-component synthesis of sulfones), or oxidized into sulfonyl chlorides and reacted with amines, then realizing a one-pot, four-component synthesis of polyfunctional sulfonamides. Using enantiomerically enriched dienes such as 1-[(R )- or 1-(S )-phenylethyloxy]-2-methyl-(E ,E )-penta-1,3-dien-3-yl isobutyrate, derived from inexpensive (R )- or (S )-1-phenylethanol, enantiomerically enriched stereotriads are obtained in one-pot operations. The latter are ready for further chain elongation. This has permitted the development of expeditious total asymmetric syntheses of important natural products of biological interest such as the baconipyrones, rifamycin S, and apoptolidin A.
- Language
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- English
- Open access status
- green
- Identifiers
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- DOI 10.1351/pac200880040791
- ISSN 1365-3075
- Persistent URL
- https://sonar.ch/global/documents/282323
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