Stereochemistry of the C-S bond cleavage in cis-2-methylcyclopentyl phenyl sulfoxide radical cation

Journal of Organic Chemistry

Volumn 74, Issue 4, 2009, Pages 1805-1808

  Baciocchi, Enrico ^a   Lanzalunga, Osvaldo ^a   Lapi, Andrea ^a   Maggini, Laura ^a  

^a SAPIENZA UNIVERSITY OF ROME   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

1 METHYLCYCLOPENTANOL; 1 METHYLCYCLOPENTYL ACETAMIDE; AROMATIC COMPOUND; CARBON; CATION; CIS 2 METHYLCYCLOPENTYL PHENYL SULFOXIDE; PHENYL BENZENETHIOSULFONATE; RADICAL; SILVER DERIVATIVE; SULFOXIDE; SULFUR; TITANIUM DIOXIDE; UNCLASSIFIED DRUG; WATER;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; OXIDATION; PHOTOCATALYSIS; PHOTOCHEMISTRY; PHOTOLYSIS; PHOTOSENSITIZATION; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY;

CARBON; CATALYSIS; CYCLOPENTANES; OXIDATION-REDUCTION; PHOTOLYSIS; STEREOISOMERISM; SULFOXIDES; SULFUR; TITANIUM;

EID: 64349103630     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo802619y     Document Type: Article

References (35)

1. Carreno, M. C. Chem. Rev. 1995, 95, 1717-1760.
2. Fernandez, I.; Khiar, N. Chem. Rev. 2003, 103, 3651-3705.
3. Clarke, M. J.; Zhu, F.; Frasca, D. R. Chem. Rev. 1999, 99, 2511.
4. Lipponer, K. G.; Vogel, E.; Keppler, B. K. Metal Based Drugs 1996, 3, 243.
5. Caligaris, M.; Carugo, O. Coord. Chem. Rev. 1996, 153, 83.
6. Shin, J. M.; Cho, Y. M.; Sachs, G. J. Am. Chem. Soc. 2004, 126, 7800-7811.
7. Legros, J.; Dehli, J. R.; Bolm, C. Adv. Synth. Catal. 2005, 347, 19-31.
8. Bentley, R. Chem. Soc. Rev. 2005, 34, 609-624.
9. Adaikalasamy, K.; Venkataramanan, N. S.; Rajagopal, S. Tetrahedron 2003, 59, 3613-3619.
10. Ganesan, M.; Sivasubramanian, V. K.; Rajagopal, S.; Ramaraj, R. Tetrahedron 2004, 60, 1921-1929.
11. Watanabe, Y.; Iyanagi, T.; Oae, S. Tetrahedron Lett. 1982, 23, 533-536.
12. Baciocchi, E.; Bietti, M.; Lanzalunga, O. Acc. Chem. Res. 2000, 33, 243-251.
13. Baciocchi, E.; Bietti, M.; Lanzalunga, O. J. Phys. Org. Chem. 2006, 19, 467-478.
14. Baciocchi, E.; Del Giacco, T.; Gerini, M. F.; Lanzalunga, O. J. Phys. Chem. A 2006, 110, 9940-9948.
15. Baciocchi, E.; Del Giacco, T.; Lanzalunga, O.; Mencarelli, P.; Procacci, B. J. Org. Chem. 2008, 73, 5675-5682.
16. (a) Baciocchi, E.; Fasella, E.; Lanzalunga, O.; Mattioli, M. Angew. Chem., Int. Ed. Engl. 1993, 32, 1071-1073.
17. (b) Shaik, S.; Reddy, A. C.; Ioffe, A.; Dinnocenzo, J. P.; Danovich, D.; Cho, J. K. J. Am. Chem. Soc. 1995, 117, 3205.
18. Dinnocenzo, J. P.; Todd, W. P.; Simpson, T. R.; Gould, I. R. J. Am. Chem. Soc. 1990, 112, 2462.
19. (a) Shaik, S.; Dinnocenzo, J. P. J. Org. Chem. 1990, 55, 3434.
20. +*/3-CN-NMQ couple is 2.72 V vs SCE, large enough to convert the aromatic sulfoxides into the corresponding radical cations.
21. Fox, M. A.; Dulay, M. T. Chem. Rev. 1993, 93, 341-357.
22. Baciocchi, E.; Rol, C.; Rosato, G. C.; Sebastiani, G. V. J. Chem. Soc., Chem. Commun. 1992, 59-60.
23. Fox, M. A.; Chen, C.-C. J. Am. Chem. Soc. 1981, 203, 6757-6759.
24. An increase in the photocurrent has been observed on decreasing the aryl methyl sulfoxide oxidation potential. Somasundaram, N.; Srinivasan, C. J. Photochem. Photobiol. A: Chem. 1998, 115, 169-173.
25. Baciocchi, E.; Del Giacco, T.; Ferrero, M. I.; Rol, C.; Sebastiani, G. V. J. Org. Chem. 1997, 62, 4015-4017.
26. +).
27. The main reaction of the sulfinyl radical is the dimerization to give phenyl benzenethiosulfonate. Chatgilialoglu, C. In The Chemistry of Sulfones and Sulfoxides; Patai, S., Rappoport, Z., Stirling, C. J. M., Eds.; John Wiley & Sons: Chicester, England, 1988; Chapter 24.
28. GC analysis of the reaction mixtures carried out before and after derivatization with the silylating agent N,O-bis(trimethylsilyl)- trifluoroacetamide (see Experimental Section) showed the absence, even in traces amounts, of cis-2-methylcyclopentanol and 2-methylcyclopentyl acetamides (comparison with authentic specimens).
29. GC analysis of 1-methylcyclopentene is hindered by the coelution of this compound with the solvent.
30. That in the heterolysis of a radical cation the two fragments can form a pair in a solvent cage has also been shown by Moiroux, Saveant, and coworkers. Anne, A.; Frauoa, S.; Moiroux, J.; Saveant, J.-M. J. Am. Chem. Soc. 1996, 118, 3938-3945.
31. -1) was estimated by the usual thermochemical cycle (details in Supporting Information).
32. Kim, C. J.; Brown, H. C. J. Am. Chem. Soc. 1972, 94, 5043-5050.
33. Imhoff, M. A.; Ragain, M.; Moore, K., Jr. J. Org. Chem. 1991, 56, 3542-3549.
34. In both ref 21 and ref 22 the possibility that hydride migration is concerted with the departure of the leaving group was dismissed. Thus, we consider that this possibility is unlikely also in our case. On the other hand, it should be considered that in the cyclopentane ring substantial energy is required to obtain the anti periplanar relationship between the C-H bond and the leaving group, which is thought to be the most convenient one for hydride migration concerted with leaving group departure.
35. Ke, B.-W.; Lin, C.-H.; Tsai, Y.-M. Tetrahedron 1997, 53, 7805-7826.