Direct Preparation of 3-Thienyl Organometallic Reagents: 3-Thienylzinc and 3-Thienylmagnesium Iodides and 3-Thienylmanganese Bromides and Their Coupling Reactions

Journal of Organic Chemistry

Volumn 62, Issue 20, 1997, Pages 6921-6927

  Rieke, Reuben D ^a   Kim, Seung Hoi ^a   Wu, Xiaoming ^a  

^a UNIVERSITY OF NEBRASKA LINCOLN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000804678     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970778b     Document Type: Article

References (40)

1. (a) Jen, K.-Y.; Miller, G. G.; Elsenbaumer, R. L. J. Chem. Soc., Chem. Commun. 1986, 1346-1347.
2. (b) Hotta, S.; Gughooputh, S. D. D. V.; Heeger, A. J.; Wudl, F. Macromolecules 1987, 20, 212-215.
3. (c) Sato, M.; Tanaka, S.; Kaeriyama, K. J. Chem. Soc., Chem. Commun. 1986, 873-874.
4. (a) Waltman, R. J.; Diaz, A. F.; Bargon, J. J. Electrochem. Soc. 1984, 131, 1452.
5. (b) Waltman, R. J.; Bargon, J. Can. J. Chem. 1986, 64, 76.
6. (a) Hartman, G. D.; Halczenko, W.; Smith, R. L.; Sugrue, M. F.; Mallogra, P. J.; Michelson, S. R.; Randall, W. C.; Schwam, H.; Sondey, J. M. J. Med. Chem. 1992, 35, 3822-3831.
7. (b) Holmes, J. M.; Lee, G. C. M.; Wijino, M.; Weinkam, R.; Wheeler, L. A.; Garst, M. E. J. Med. Chem. 1994, 37, 1646-1651.
8. (a) Gronowitz, S.; Hakansson, R. Arkiv. Kemi. 1959, 17, 73-82.
9. (b) Gronowitz, S. In Organic Sulphur Chemistry-Structure, Mechanism, and Synthesis; Sterling, C. J. M., Ed.; Butter-worths: London, 1975; pp 203-228.
10. (a) Zhang, Y.; Hornfeldt, A.-B.; Gronowitz, S. J. Heterocycl. Chem. 1995, 32, 435-444.
11. (b) Ritter, S. K.; Noftle, R. E. Chem, Mater. 1992, 4, 872-879.
12. (c) Arnswald, M.; Neumann, W. P. J. Org. Chem. 1993, 58, 7022-7028.
13. (d) Jaysuriya, N.; Kagan, J. Heterocycles 1986, 24, 2261-2264.
14. (e) Yamamura, K.; Miyake, H.; Nakatsuji, S. Chem. Lett. 1992, 1213-1216.
15. (f) Gronowitz, S. Arkiv. Kemi. 1958, 12, 533-545.
16. (a) Ritter, S. K; Noftle, R. E. Chem. Mater. 1992, 4, 872.
17. (b) Frohlich, H.; Kalt, W. J. Org. Chem. 1990, 55, 2993.
18. (c) Gronowitz, S. Adv. Heterocycl. Chem. 1963, 1, 75.
19. Reviews about active metals: (a) Rieke, R. D. Science 1989, 24, 1260-1264. (b) Furstner, A. Angew. Chem., Int. Ed. Engl. 1993, 92, 164-189 and references cited therein.
20. Reviews about active metals: (a) Rieke, R. D. Science 1989, 24, 1260-1264. (b) Furstner, A. Angew. Chem., Int. Ed. Engl. 1993, 92, 164-189 and references cited therein.
21. (a) Zhu, L.; Wehmeyer, M.; Rieke, R. D. J. Org. Chem. 1991, 56, 1445-1453.
22. (b) Xiong, H.; Rieke, R. D. J. Org. Chem. 1989, 54, 3247-3252.
23. (c) Rochfort, G. L.; Rieke, R. D. Inorg. Chem. 1986, 25, 348-355.
24. (d) Rieke, R. D. Top Curr. Chem. 1975, 59, 1
25. (e) Rieke, R. D.; Wehmeyer, R, M.; Wu, T.-C.; Ebert, G. W. Tetrahedron 1989, 45, 443-454.
26. Rieke, R, D.; Hudnall, P. M.; Uhm, S. J. Chem. Soc., Chem. Commun. 1973, 269.
27. Kim, S. H.; Hanson, M. V.; Rieke, R. D. Tetrahedron Lett. 1996, 37, 2197-2200.
28. Gosmin, C.; Nedlec, J. Y.; Perichon, J. Tetrahedron Lett. 1997, 38, 1941-1942.
29. Wu, X.; Rieke, R. D. J. Org. Chem., 1995, 60, 6658-6659.
30. (a)Chen, T.; Rieke, R. D. J. Am. Chem. Soc. 1992, 114, 10087-10088.
31. (b) Sakamoto, T.; Kondo, Y.; Murata, N.; Yamanaka, H. Tetrahedron Left. 1992, 33, 5373-5374.
32. (c) Sakamoto, T.; Kondo, Y.; Murata, N.; Yamanaka, H. Tetrahedron Lett. 1993, 34, 5955-5956.
33. Kim, S. H.; Rieke, R. D. Tetrahedron Lett. 1997, 38, 993-996.
34. 3-Iodothiophene is easily prepared via iodination of room temperature stable 3-lithiothiophene using 1,2-diiodoethane at ambient temperature: Wu, X.; Chen. T.-A.; Zhu, L.; Rieke, R. D. Tetrahedron Lett. 1994, 35, 3673-3674.
35. Although 3-thienylmagnesium bromide was prepared via metathesis of 3-lithiophene with magnesium bromide in ethyl ether as described in refs 5d-f, the room temperature regiostability of the Grignard reagent was not discussed.
36. 13C NMR δ 142.3, 135.8, 128.8, 127.1, 126.4, 126.3, 126.2, 120.2. See: Chen, T.-A. Ph.D. Dissertation, University of Nebraska-Lincoln, 1994, p 52.
37. (a) For a general review of organomanganese reagents, see: Normant, J. F.; Cahiez, G. Modern Synthetic Methods; John Wiley & Sons Inc.: Chichester, 1983, Vol. 3, pp 172-216 and references cited therein.
38. 13C NMR δ 189.91, 141.19, 138.52, 133.84, 132.23, 129.27, 128.50, 128.28, 126.13. For 5a: see Experimental Section.
39. The formation of bis-organomanganese bromides cannot be ruled out on the basis our gas chromatography monitoring. After acidic quenching of the reaction mixture followed by gas chromatography analysis, less than 5% of thiophene was detected.
40. 1,2-Dibromoethane was used to consume the remaining active manganese in the reaction mixture because Mn* was active to additional electrophile to give a homocoupling product.