The Chemistry of the Thiosulfinyl Group: Preparation, Structure, and Spectroscopic and Chemical Properties of Cyclic Thionosulfites
Juzo Nakayama
Department of Chemistry, Faculty of Science, Saitama University, Sakura-ku, Saitama, Saitama 338-8570, Japan (phone and fax: +81 48-858-3390)
Search for more papers by this authorSanae Yoshida (nee Tanaka)
Department of Chemistry, Faculty of Science, Saitama University, Sakura-ku, Saitama, Saitama 338-8570, Japan (phone and fax: +81 48-858-3390)
Search for more papers by this authorYoshiaki Sugihara
Department of Chemistry, Faculty of Science, Saitama University, Sakura-ku, Saitama, Saitama 338-8570, Japan (phone and fax: +81 48-858-3390)
Search for more papers by this authorAkira Sakamoto
Department of Chemistry, Faculty of Science, Saitama University, Sakura-ku, Saitama, Saitama 338-8570, Japan (phone and fax: +81 48-858-3390)
Search for more papers by this authorJuzo Nakayama
Department of Chemistry, Faculty of Science, Saitama University, Sakura-ku, Saitama, Saitama 338-8570, Japan (phone and fax: +81 48-858-3390)
Search for more papers by this authorSanae Yoshida (nee Tanaka)
Department of Chemistry, Faculty of Science, Saitama University, Sakura-ku, Saitama, Saitama 338-8570, Japan (phone and fax: +81 48-858-3390)
Search for more papers by this authorYoshiaki Sugihara
Department of Chemistry, Faculty of Science, Saitama University, Sakura-ku, Saitama, Saitama 338-8570, Japan (phone and fax: +81 48-858-3390)
Search for more papers by this authorAkira Sakamoto
Department of Chemistry, Faculty of Science, Saitama University, Sakura-ku, Saitama, Saitama 338-8570, Japan (phone and fax: +81 48-858-3390)
Search for more papers by this authorAbstract
Treatment of the tetrahydrothiophene-3,4-diol 5 with 1,1′-thiobis-(1H-benzimidazole) (6) furnished two diastereoisomers of the novel cyclic thionosulfite 4 with different configurations at the pseudo-tetrahedral center of the thiosulfinyl (SS) group. The configuration of the SS group of the major diastereoisomer (isolated in 45% yield) was established to be syn to the thiolane ring, as determined by X-ray crystallographic analysis, while that of the minor diastereoisomer (isolated in 10% yield) was anti. 1H-NMR Spectroscopic analysis clarified that the shielding and deshielding zones of the SS group are similar to those of the well-documented SO group. Characteristic absorptions of the SS group in the IR, Raman, and UV/VIS spectra were assigned on the basis of calculations at the B3LYP/6-31G* level. The reactivity of the SS group toward thermolysis, hydrolysis, and oxidation was examined. The SS group is more resistant toward oxidation than the divalent sulfide S-atom, but is oxidatively converted to the SO group.
References
- 1 G. W. Kutney, K. Turnbull, Chem. Rev. 1982, 82, 333.
- 2 R. L. Kuczkowski, E. B. Wilson Jr., J. Am. Chem. Soc. 1963, 85, 2028; R. L. Kuczkowski, J. Am. Chem. Soc. 1963, 85, 3047; R. L. Kuczkowski, J. Am. Chem. Soc. 1964, 86, 3617.
- 3a Q. E. Thompson, M. M. Crutchfield, M. W. Dietrich, J. Org. Chem. 1965, 30, 2696;
- 3b G. K. Abdullaev, I. A. Mamedov, M. M. Mamedov, Azerb. Khim. Zh. 1973, 5–6, 43;
- 3c K. Miaskiewicz, R. Steudel, J. Chem. Soc., Dalton Trans. 1991, 2395;
- 3d R. Steudel, Y. Drozdova, K. Miaskiewicz, R. H. Hertwig, W. Koch, J. Am. Chem. Soc. 1997, 119, 1990.
- 4a D. N. Harpp, K. Steliou, C. J. Cheer, J. Chem. Soc., Chem. Commun. 1980, 825;
- 4b J. P. Snyder, N. Nevins, S. L. Tardif, D. N. Harpp, J. Am. Chem. Soc. 1997, 119, 12685;
- 4c E. Zysman-Colman, C. B. Abrams, D. N. Harpp, J. Org. Chem. 2003, 68, 7059.
- 5
F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen, R. Taylor, J. Chem. Soc., Perkin Trans. 2 1987, S1.
10.1039/p298700000s1 Google Scholar
- 6 S. C. Abrahams, Acta Crystallogr. 1955, 8, 661.
- 7 F. Iwasaki, Acta Crystallogr., Sect. B 1979, 35, 2099; C. Tamura, K. Aiba, S. Sato, T. Hata, S. Morimura, T. Yoshioka, Acta Crystallogr., Sect. B 1977, 33, 3918.
- 8 F. Rebiere, O. Samuel, L. Ricard, H. B. Kagan, J. Org. Chem. 1991, 56, 5991.
- 9 J. Nakayama, S. Yamaoka, M. Hoshino, Tetrahedron Lett. 1988, 29, 1161; J. Nakayama, R. Hasemi, K. Yoshimura, Y. Sugihara, S. Yamaoka, J. Org. Chem. 1998, 63, 4912.
- 10 D. N. Harpp, K. Steliou, T. H. Chan, J. Am. Chem. Soc. 1978, 100, 1222.
- 11 S. Tanaka, Y. Sugihara, A. Sakamoto, A. Ishii, J. Nakayama, J. Am. Chem. Soc. 2003, 125, 9024.
- 12 G. Mitchell, in ‘Comprehensive Heterocyclic Chemistry II’, Ed. R. C. Storr, Pergamon Press, Oxford, 1996, Vol. 4, Chapt. 4.15.
- 13 S. Tanaka, Y. Sugihara, A. Sakamoto, A. Ishii, J. Nakayama, Heteroat. Chem. 2003, 14, 587.
- 14 T. Benincori, E. Brenna, F. Sannicolò, L. Trimarco, P. Antognazza, E. Cesarotti, F. Demartin, T. Pilati, G. Zotti, J. Organomet. Chem. 1997, 529, 445.
- 15 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, USA, 1998.
- 16 C. H. Green, D. G. Hellier, J. Chem. Soc., Perkin Trans. 2 1972, 458; C. H. Green, D. G. Hellier, J. Chem. Soc., Perkin Trans. 2 1973, 243; J. G. Pritchard, P. C. Lauterbur, J. Am. Chem. Soc. 1961, 83, 2105; C. H. Green, D. G. Hellier, J. Chem. Soc., Perkin Trans. 2 1975, 190; G. W. Buchanan, D. G. Hellier, Can. J. Chem. 1976, 54, 1428.
- 17 C. R. Johnson, D. McCants Jr., J. Am. Chem. Soc. 1965, 87, 1109; G. Barbieri, M. Cinquini, S. Colonna, F. Montanari, J. Chem. Soc. C 1968, 659; W. O. Siegl, C. R. Johnson, J. Org. Chem. 1970, 35, 3657; E. Block, E. J. Corey, R. E. Penn, T. L. Renken, P. F. Sherwin, J. Am. Chem. Soc. 1976, 98, 5715; I. Jalsovszky, F. Ruff, M. Kajtár-Peredy, A. Kucsman, Synthesis 1990, 1037; D. V. Deubel, J. Org. Chem. 2001, 66, 2686; T. Patonay, W. Adam, A. Lévai, P. Kövér, M. Németh, E.-M. Peters, K. Peters, J. Org. Chem. 2001, 66, 2775.
- 18 I. A. Abu-Yousef, D. N. Harpp, J. Org. Chem. 1997, 62, 8366; S. L. Tardif, A. Z. Rys, C. B. Abrams, I. A. Abu-Yousef, P. B. F. Lesté-Lasserre, E. K. V. Schultz, D. N. Harpp, Tetrahedron 1997, 53, 12225.
- 19 R. S. Berry, J. Chem. Phys. 1960, 32, 933; S. Oae, M. Yokoyama, M. Kise, N. Furukawa, Tetrahedron Lett. 1968, 4131; P. Gillespie, P. Hoffman, H. Klusacek, D. Marquarding, S. Pfohl, F. Ramirez, E. A. Tsolis, I. Ugi, Angew. Chem., Int. Ed. 1971, 10, 687; S. Oae, T. Kawai, N. Furukawa, F. Iwasaki, J. Chem. Soc., Perkin Trans. 2 1987, 405; N. Furukawa, T. Shibutani, H. Fujihara, Tetrahedron Lett. 1987, 5845.
- 20 A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C. Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori, R. Spagna, J. Appl. Crystallogr. 1999, 32, 115.
- 21 G. M. Sheldrick, SHELXL 97, Program for the Refinement of Crystal Structures, 1997.
- 22 R. H. Blessing, Acta Crystallogr., Sect. A 1995, 51, 33.
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