A novel sulfinylation of alkenes by tosyl cyanide with titanium(IV) chloride

Tetrahedron Letters

Volumn 40, Issue 26, 1999, Pages 4857-4860

  Morgan, Paul E ^a   McCague, Ray ^a,b   Whiting, Andrew ^a  

^a UNIVERSITY OF MANCHESTER   (United Kingdom)

^b Chiroscience Ltd   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; CHLORINE DERIVATIVE; CYANIDE; SILICA GEL; SULFOXIDE; TITANIUM DERIVATIVE; TOSYLCYANIDE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; STEREOSPECIFICITY;

EID: 0033603482     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)00894-1     Document Type: Article

References (16)

1. a) "Hetero Diels-Alder Methodology in Organic Synthesis", Boger, D.L.; and Weinreb, S.M.; Organic Chemistry Monographs; Vol. 47, Academic Press, San Diego, 1987;
2. b) Meyers, A.I.; in "The chemistry of the cyano group", Patai, S.; and Rappoport, Z.; Interscience, London, 1970, 356;
3. c) Rüffer, U.; and Breitmair, E.; Synth., 1989, 623;
4. d) Weinreb, S.M.; and Smith, R.R.; Tetrahedron, 1982, 38, 3087;
5. e) Pews, P.G.; Nyquist, E.B.; and Corson, F.P.; J. Org. Chem., 1970, 35, 4096;
6. f) Jagt, J.C.; and Van Leusen, A.M.; Recl. Trav. Chim. Pays-bas, 1973, 82, 1343;
7. g) idem, J. Org. Chem., 1974, 39, 564;
8. h) Daluge, S.; and Vince, R.; J. Org. Chem., 1978, 43, 2311.
9. Morgan, P.E.; McCague, R.; and Whiting, A.; J. Chem. Soc., Chem. Commun., 1996, 1811.
10. 2AlCl and racemic binaphthol, a 20 % yield of the [2+2]-adduct 2 was obtained, but none of the normal product 3: Morgan, P.E.; McCague, R.; and Whiting, A.; unpublished results.
11. Malpass, J.R.; and Tweddle, N.J.; J. Chem. Soc., Perkin Trans., 1, 1977, 874.
12. 1H n.m.r. data, δ: 5 (from cyclopentene) 3.75 (1H, m, CH.SO), 4.20 (1H, dt, J 8 and 3 Hz, CH.Cl); 5 (from cyclohexene) 3.65 (1H, m, CH.SO), 4.12 (1H, dt, J 5 and 10 Hz, CH.Cl); 6c 3.32 (1H, dt, J 7 and 4 Hz, CH.SO), 4.08 (1H, m, CH.OH); 6d 2.59 (1H, dt, J 5 and 10 Hz, CH.SO), 3.19 (1H, dt, J 5 and 10 Hz, CH.OH); 7a 3.50-3.56 (1H, m, CH.SO), 5.03 (1H, dt, J 6 and 3 Hz, CH.OAc); 7b 3.04 (1H, dt, J 9 and 4 Hz, CH.SO), 4.75 (1H, dt, J 9 and 4 Hz, CH.OAc).
13. The regiospecific formation of 5a and 5b is indicated by the fact that direct elimination (NaOH) results of clean unambiguous formation of the corresponding E-vinylsulfoxides 8 and 9 respectively: Morgan, P.E.; McCague, R.; and Whiting, A.; unpublished results. (equation presented)
14. 2, which supports the idea of formation of a titanium(IV) isocyanate complex.
15. a) Vorob'eva, I.S.; and Stadnichuk, M.D.; Zh. Obsch. Khim., 1984, 54, 2064;
16. b) Glaros, G.; and Sullivan, S.; Synth. Commun., 1976, 6, 495.