tert-butylsulfonamide. A new nitrogen source for catalytic aminohydroxylation and aziridination of olefins

Organic Letters

Volumn 1, Issue 5, 1999, Pages 783-786

  Gontcharov, Alexander V ^a   Liu, Hong ^a   Sharpless, K Barry ^a  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

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Indexed keywords

EID: 0005498666     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol990761a     Document Type: Article

References (24)

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2. (b) Li, G.; Chang, H.-T.; Sharpless, K. B. Angew. Chem., Int. Ed. Engl. 1996, 35, 451.
3. (c) Rubin, A. E.; Sharpless, K. B. Angew. Chem., Int. Ed. Engl. 1997, 36, 2637.
4. (d) Pringle, W.; Sharpless, K. B. Tetrahedron Lett. 1999, in press.
5. (e) Jeong, J. U.; Tao, B.; Sagasser, I.; Henniges, H.; Sharpless, K. B. J. Am. Chem. Soc. 1998, 120, 6844
6. Fukuyama, T.; Jow, C.-K.; Cheung, M. Tetrahedron Lett. 1995, 36, 6373.
7. (a) Pringle, W.; Rubin, A. E.; Sharpless, K. B. Unpublished results.
8. (b) However, the nosyl chloramines give excellent results in the stoichiometric selenium-mediated allylic amination (see ref 1a).
9. Sun, P.; Weinreb, S. M. J. Org. Chem. 1997, 62, 8604.
10. Stetter, H.; Krause, M.; Last, W.-D. Chem. Ber. 1969, 102, 3357.
11. (a) Oppolzer, W.; Wills, M.; Starkemann, C.; Bernardinelli, G. Tetrahedron Lett. 1990, 31, 4117.
12. (b) Martinez-Merino, V.; Gil, M. J.; Zabalza, J. M.; Gonzalez, A. Heterocycles 1995, 41, 2737.
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14. Hovius, K.; Engberts, B. F. N. Tettrahedron Lett. 1972, 181.
15. Maricich, T. J.; Hoffman, V. L. J. Am. Chem. Soc. 1974, 96, 7770.
16. 7 162-165°C).
17. 11 10 mL), and benzene (250 mL) were stirred for 10 min at 50°C on a water bath. Then the remainder of the TBHP solution (146 mL, 0.60 mol total) was added slowly so that the temperature inside the reaction flask did not rise above 80°C. After the addition was complete, the mixture was stirred at 60°C for 1 h (completion of the reaction was checked by TLC and/or GC) and then chilled in an ice bath. The excess of TBHP was destroyed by treating the mixture with a saturated aqueous solution of sodium metabisulfite (exothermic reaction!). The organic phase was separated and washed with saturated aqueous sodium bicarbonate and brine and then dried with magnesium sulfate. The crude product was isolated in 95% yield (92 g) by evaporating the solvents in a vacuum. The product thus obtained contained traces of unreacted disulfide as the only impurity, and it was used in the subsequent step without further purification. (b) To a solution of terr-butyl tert-butanethiosulfinate (124 g, 0.64 mol) in 300 mL of methylene chloride, chilled in ice, was added slowly a solution of sulfuryl chloride (86 g, 0.64 mol) in 50 mL of methylene chloride. The resulting yellow solution was stirred for 1 h allowing it to gradually reach room temperature. At this point NMR analysis revealed no starting material remaining. The solvent and volatile byproducts of the reaction were removed under aspirator vacuum at room temperature (stench!). The product was isolated by fractional distillation of the remaining oil (boiling range 65-69°C at 24 mmHg). Yield: 67 g (75%) as a pale yellow oil. Occasionally, the distilled tert-butylsulfinyl chloride was contaminated with side products (most probably, sulfur chlorides), which gave it a deeper yellow or even orange color. The presence of these impurities did not affect the outcome of the next step (ref 9).
18. Sharpless, K. B.; Verhoeven, T. R. Aldrichimica Acta 1979, 12, 63.
19. 15 revealed an available chlorine content of 35.1% (theor. 36.6%).
20. Rudolph, J.; Sennhenn, P. C.; Vlaar, C. P.; Sharpless, K. B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2810.
21. Mintz, M. J.; Walling, C. Organic Syntheses; Wiley: New York, 1973; Collect. Vol. V, p 184.
22. Mintz, M. J.; Walling, C. Organic Syntheses; Wiley: New York, 1973; Collect. Vol. V, p 184.
23. Titration was performed by following the protocol established for Chloramine T: Reagent Chemicals: American Chemical Society Specifications, 8th ed.; American Chemical Society: Washington, DC, 1993; pp 242-244.
24. All the new compounds were characterized using proton and carbon NMR spectra whose key features closely matched those for the previously reported N-tosyl analogues.