Pyridine N-oxide catalyzed thione-to-thiol rearrangement of xanthates. MO analysis of the reaction mechanism

Tetrahedron

Volumn 54, Issue 32, 1998, Pages 9333-9340

  Nakagawa, Hidetoshi ^a   Eto, Masashi ^a   Harano, Kazunobu ^a  

^a KUMAMOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

PYRIDINE 1 OXIDE; XANTHIC ACID DERIVATIVE;

ARTICLE; CATALYST; DRUG SYNTHESIS; GENE REARRANGEMENT; NONHUMAN; NUCLEAR MAGNETIC RESONANCE; PRIORITY JOURNAL; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 0032490988     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(98)00578-X     Document Type: Article

References (14)

1. 1. a) Harano, K.; Nakagawa, H.; Kamei, K.; Kiyonaga H.; Hisano, T. Chem. Pharm. Bull., 1992, 40, 1675.
2. b) Harano, K.; Nakagawa, H.; Kiyonaga H.; Hisano, T. Org. Prep. Proced.Int, 1992, 24, 200.
3. c) 1-Methoxypyridine iodide showed low catalytic reactivity toward xanthates, indicating that the rearrangement is not brought about by the alkylation of 1-methoxypyridine derivative.
4. d) Taguchi, T.; Kiyoshima, Y.; Komori, O.; Mori, M. Tetrahedron Lett., 1969, 3631.
5. 2. Yoshida H., Bull. Chem. Soc. Jpn,. 1969, 42, 1948 and references cited herein.
6. 3. a) Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Stewart, J. J. P. J. Am. Chem. Soc., 1985, 107, 3902.
7. b) Stewart, J. J. P. J. Comp. Chem., 1989, 10, 209; Stewart, J. J. P. J. Comp. Chem., 1989, 10, 221.
8. b) Stewart, J. J. P. J. Comp. Chem., 1989, 10, 209; Stewart, J. J. P. J. Comp. Chem., 1989, 10, 221.
9. c) Stewart, J. J. P. QCPE Bull., 1989, 9, 10.
10. 4. Gaussian 94, Revision D.4, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson; G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A.; Gaussian, Inc., Pittsburgh PA, 1995.
11. 5. The PM3 calculation of dimethyl xanthate showed the existence of two local minimum conformations. The methyl groups lie within a plane of -O(C=S)S-group with syn/anti dispositions with regard to the C=S bond. The anti conformation which is global minimum is ca. 1.6 kcal/mol more stable than the syn conformation. However ab initia calculation (RHF/6-31G*) gave opposite prediction (syn). This structure is in accordance with those observed in the X-ray crystal structures of the analogous compounds. Abrahamson, S.; Innes, M. Acta Crystallogr. Sc., 1974, 30, 721; B. Dahlen, Acta. Chem. Scand. Ser., 1977, 31, 407.
12. 5. The PM3 calculation of dimethyl xanthate showed the existence of two local minimum conformations. The methyl groups lie within a plane of -O(C=S)S-group with syn/anti dispositions with regard to the C=S bond. The anti conformation which is global minimum is ca. 1.6 kcal/mol more stable than the syn conformation. However ab initia calculation (RHF/6-31G*) gave opposite prediction (syn). This structure is in accordance with those observed in the X-ray crystal structures of the analogous compounds. Abrahamson, S.; Innes, M. Acta Crystallogr. Sc., 1974, 30, 721; B. Dahlen, Acta. Chem. Scand. Ser., 1977, 31, 407.
13. 6. To save the CPU time, the time-consuming IRC calculations were performed by PM3 and AM1 methods.
14. 7. Similar CT bands were observed in the UV-Vis absorption spectra of N-alkylpyridinium iodide in various solvents. Kosower, E. M. J. Am. Chem. Soc., 1958, 80, 3253, 3261, 3267.