The Chiral S-N Axis in Sulfenamides: Enantiomeric Resolution, Direct Demonstration of Optical Activity, and Kinetics of Interconversion

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 20, 1997, Pages 2216-2219

  Blanca, Merav Ben David ^a   Maimon, Eric ^a   Kost, Daniel ^a  

^a BEN GURION UNIVERSITY OF THE NEGEV   (Israel)

Author keywords

Chirality; Enantiomeric resolution; NMR spectroscopy; Restricted rotation; Sulfenamides

Indexed keywords

EID: 0030668014     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199722161     Document Type: Article

References (19)

1. Reviews on sulfenamide chemistry: a) D. Kost, M. Raban in The Chemistry of Sulphenic Acids and their Derivatives (Ed.: S. Patai), Wiley, Chichester, 1990, pp. 23-82; b) M. Raban D. Kost in Acyclic Organonitrogen Stereodynamics (Eds.: J. B. Lambert, Y. Takeuchi), VCH, New York, 1992, pp. 57-88; c) Tetrahedron 1984, 40, 3345-3381; d) L. Craine, M. Raban, Chem. Rev. 1989, 89, 689-712.
2. Reviews on sulfenamide chemistry: a) D. Kost, M. Raban in The Chemistry of Sulphenic Acids and their Derivatives (Ed.: S. Patai), Wiley, Chichester, 1990, pp. 23-82; b) M. Raban D. Kost in Acyclic Organonitrogen Stereodynamics (Eds.: J. B. Lambert, Y. Takeuchi), VCH, New York, 1992, pp. 57-88; c) Tetrahedron 1984, 40, 3345-3381; d) L. Craine, M. Raban, Chem. Rev. 1989, 89, 689-712.
3. Reviews on sulfenamide chemistry: a) D. Kost, M. Raban in The Chemistry of Sulphenic Acids and their Derivatives (Ed.: S. Patai), Wiley, Chichester, 1990, pp. 23-82; b) M. Raban D. Kost in Acyclic Organonitrogen Stereodynamics (Eds.: J. B. Lambert, Y. Takeuchi), VCH, New York, 1992, pp. 57-88; c) Tetrahedron 1984, 40, 3345-3381; d) L. Craine, M. Raban, Chem. Rev. 1989, 89, 689-712.
4. Reviews on sulfenamide chemistry: a) D. Kost, M. Raban in The Chemistry of Sulphenic Acids and their Derivatives (Ed.: S. Patai), Wiley, Chichester, 1990, pp. 23-82; b) M. Raban D. Kost in Acyclic Organonitrogen Stereodynamics (Eds.: J. B. Lambert, Y. Takeuchi), VCH, New York, 1992, pp. 57-88; c) Tetrahedron 1984, 40, 3345-3381; d) L. Craine, M. Raban, Chem. Rev. 1989, 89, 689-712.
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8. Atkinson et al. isolated diastereomers with one asymmetric carbon center and a sulfenamide bond. However, it was argued that the second stereogenic unit responsible for the observation of diastereomers was the N-N bond, which was also present: R. S. Atkinson, B. D. Judkins, B. H. Patwardhan, Tetrahedron Lett. 1978, 3137-3140.
9. Chiroptical measurements of diastereomeric stereolabile sulfenamides also containing an asymmetric carbon center were reported: M. Raban, S. K. Lauderback, J. Am. Chem. Soc. 1971, 93, 2781-2783. However, optical activity could not be assigned directly to one or the other stereogenic unit.
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14. c) for the definition of absolute configuration in a chiral axis see V. Prelog, G. Helmchen. Angew. Chem. 1982, 94, 614-631; Angew. Chem. Int. Ed. Engl. 1982, 21, 567-583.
15. K. G. Orrell, V. Sik, Annu. Rep. NMR Spectrosc. 1993, 27, 103-171.
16. The possible effect of UV and polarized light on the rate of rotation about the S-N bond is being studied further.
17. G. A. Olah, L. Ohannesian, M. Arvanaghi, G. K. Surya Prakash. J. Org. Chem. 1984, 49, 2032-2034.
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19. M. Kuroki, Y. Tsunashima, J. Heterocycl. Chem. 1981, 18, 709-714.