Rhodium catalysed S- and SO-transfer: Novel syntheses of norbornane episulfoxides and episulfides

Synlett

Volumn , Issue 4, 1998, Pages 391-392

  Kendall, Jackie D ^a   Simpkins, Nigel S ^a  

^a UNIVERSITY OF NOTTINGHAM   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0002420348     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1998-1665     Document Type: Article

References (15)

1. For a recent example, see Dybowski, P.; Skowronska, A. Synthesis 1997, 1134.
2. Adam, W.; Weinkötz, S. J. Chem. Soc., Chem. Commun. 1996, 177.
3. Adam, W.; Deeg, O.; Weinkötz, S. J. Org. Chem. 1997, 62, 7084.
4. Singlet SO has been generated at 12 K in an argon matrix; reaction with allene or dimethylacetylene appeared to give episulfoxide products, as indicated by IR spectroscopy, see Salama, F.; Frei, H. J. Phys. Chem. 1989, 93, 1285.
5. Abu-Yousef, I. A.; Harpp, D. N. J. Org. Chem. 1997, 62, 8366.
6. Blake, A. J.; Westaway, S. M.; Simpkins, N. S. Synlett 1997, 919.
7. Bonini, B. F.; Maccagnani, G.; Mazzanti, G. J. Chem. Soc., Chem. Commun. 1976, 431.
8. Typically, temperatures of around 100 °C are quoted for decomposition of the parent ethylene episulfoxide (see reference 7); the use of refluxing toluene is reported as optimal in the case of episulfoxide 3 (see reference 5).
9. Heyke, O.; Neher, A.; Lorenz, I-P. Z. Anorg. Allg. Chem. 1992, 608, 23.
10. 2Pd(SO) was less satisfactory in our hands due to oxidation of phosphine ligands. For a review of sulfur oxides as ligands in co-ordination compounds, see Schenk, W. A. Angew. Chem. Int. Ed. Engl. 1987, 26, 98.
11. 10OS requires M+H, 143.0531).
12. 1H NMR data for sulfide 9 with data reported earlier. Our data matches that for the exo-isomer, the corresponding endo-isomer being reported as giving very distinct data, see Emsley, J.; Griffiths, D. W.; Jayne, G. J. J. J. Chem. Soc., Perkin Trans. 1 1979, 228. Oxone oxidation of this known exo-sulfide gives episulfoxide identical with 6b obtained as shown in Scheme 1.
13. Johnson, P.; Taylor, R. J. K. Tetrahedron Lett. 1997, 38, 5873.
14. 3S requires M+H, 173.0272).
15. 4 (2.3 mg, 0.0052 mmol) was heated to reflux in toluene (1.5 ml) for 22h. After cooling the solvent was evaporated, a small volume of petroleum ether added, and the solution filtered through silica-gel to give 8 (28 mg, 39%).