Two-directional annelation: Dual benzyne cycloadditions starting from bis(sulfonyloxy)diiodobenzene

Angewandte Chemie - International Edition

Volumn 45, Issue 41, 2006, Pages 6842-6844

  Hamura, Toshiyuki ^a   Arisawa, Tetsu ^a   Matsumoto, Takashi ^a   Suzuki, Keisuke ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

Arynes; Chemoselectivity; Cycloaddition; Polycycles; Regioselectivity

Indexed keywords

ADDITION REACTIONS; HALOGEN COMPOUNDS; REACTION KINETICS;

ARYNES; CHEMOSELECTIVITY; CYCLOADDITION; POLYCYCLES; REGIOSELECTIVITY;

AROMATIC COMPOUNDS;

EID: 33750475201     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200602539     Document Type: Article

References (32)

1. K. P. C. Vollhardt, Angew. Chem. 1984, 96, 525-541;
2. Angew. Chem. Int. Ed. Engl. 1984, 23, 539-556.
3. For reviews on arynes, see: a) R. W. Hoffmann, Dehydrobenzene and Cycloalkynes, Academic, New York, 1967;
4. b) S. V. Kessar in Comprehensive Organic Synthesis, Vol. 4 (Ed.: B. M. Trost), Pergamon, Oxford, UK, 1991, pp. 483-515;
5. c) H. Pellissier, M. Santelli, Tetrahedron 2003, 59, 701-730;
6. d) H. H. Wenk, M. Winkler, W. Sander, Angew. Chem. 2003, 115, 518-546;
7. Angew. Chem. Int. Ed. 2003, 42, 502-528.
8. Use of this reactive species, even as its synthetic equivalents, has been quite limited; for pioneering studies on the generation and trapping of 1,4-benzdiyne equivalents, see: a) H. Hart, D. Ok, J. Org. Chem. 1986, 51, 979-986;
9. b) H. Hart, C.-Y. Lai, G. Nwokogu, S. Shamouilian, A. Teuerstein, C. Zlotogorski, J. Am. Chem. Soc. 1980, 102, 6649-6651;
10. for other recent examples, see: c) Y.-L. Chen, J.-Q. Sun, X. Wei, W.-W. Wong, A. W. M. Lee, J. Org. Chem. 2004, 69, 7190-7197;
11. d) G. E. Morton, A. G. M. Barrett, J. Org. Chem. 2005, 70, 3525-3529;
12. e) I. I. Schuster, L. Cracium, D. M. Ho, R. A. Pascal, Jr., Tetrahedron 2002, 58, 8875-8882;
13. f) H. M. Duong, M. Bendikov, D. Steiger, Q. Zhang, G. Sonmez, J. Yamada, F. Wudl, Org. Lett. 2003, 5, 4433-4436.
14. a) T. Matsumoto, T. Hosoya, M. Katsuki, K. Suzuki, Tetrahedron Lett. 1991, 32, 6735-6736;
15. b) T. Hosoya, E. Takashiro, T. Matsumoto, K. Suzuki, J. Am. Chem. Soc. 1994, 116, 1004-1015.
16. T. Matsumoto, T. Sohma, S. Hatazaki, K. Suzuki, Synlett 1993, 843-846.
17. a) T. Hosoya, T. Hasegawa, Y. Kuriyama, T. Matsumoto, K. Suzuki, Synlett 1995, 177-179;
18. b) T. Hosoya, T. Hamura, Y. Kuriyama, K. Suzuki, Synlett 2000, 520-522;
19. c) T. Hamura, T. Hosoya, H. Yamaguchi, Y. Kuriyama, M. Tanabe, M. Miyamoto, Y. Yasui, T. Matsumoto, K. Suzuki, Helv. Chim. Acta 2002, 85, 3589-3604.
20. We recently reported a viable route to functionalized tricyclo-butabenzenes by exploiting benzyne-KSA [2+2] cycloaddition chemistry; see: a) T. Hamura, Y. Ibusuki, H. Uekusa, T. Matsumoto, K. Suzuki, J. Am. Chem. Soc. 2006, 128, 3534-3535;
21. b) T. Hamura, Y. Ibusuki, H. Uekusa, T. Matsumoto, J. S. Siegel, K. K. Baldridge, K. Suzuki, J. Am. Chem. Soc. 2006, 128, 10 032-10 033.
22. See the Supporting Information for details.
23. Recently, the related chemoselective generation of polyfunctionalized arynes by I-Mg exchange of 2-iodophenyl sulfonates was developed; see: a) I. Sapountzis, W. Lin, M. Fisher, P. Knochel, Angew. Chem. 2004, 116, 4464-4466;
24. Angew. Chem. Int. Ed. 2004, 43, 4364-4366;
25. b) W. Lin, I. Sapountzis, P. Knochel, Angew. Chem. 2005, 117, 4330-4333;
26. Angew. Chem. Int. Ed. 2005, 44, 4258-4261.
27. For related regioselective halogen-lithium exchange of dihalobenzenes, see: M. Dabrowski, J. Kubicka, S. Lulinski, J. Serwatowski, Tetrahedron 2005, 61, 6590-6595.
28. When the same reaction was performed in THF, mono-cycloadduct 3 and bis-cycloadduct 5 were obtained (52 and 10%, respectively).
29. R. Gray, L. G. Harruff, J. Krymowski, J. Peterson, V. Boekelheides, J. Am. Chem. Soc. 1978, 100, 2892-2893.
30. 2O as solvent led to a lower yield of 11 (71%), presumably as a result of the low solubility of the initially formed mono-cycloadduct.
31. 2O.
32. The following order of reactivity was assessed by a competition experiment: nitrone 10 > KSA 2 > furan (8). The reaction of alkoxybenzyne with the same amount of 2, 10, and 8 gave the [2+3] cycloadduct (56%), the [2+2] cycloadduct (30%), and the [2+4] cycloadduct (13%), respectively (see the Supporting Information).