Preparation and coupling reaction of thienylmanganese bromides

Tetrahedron Letters

Volumn 38, Issue 6, 1997, Pages 993-996

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

^a UNIVERSITY OF NEBRASKA LINCOLN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

THIOPHENE DERIVATIVE;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; IN VITRO STUDY; METHODOLOGY; REACTION ANALYSIS;

EID: 0031562088     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(96)02507-5     Document Type: Article

References (28)

1. 1. Kim, S. H.; Hanson, M. V.; Rieke, R. D. Tetrahedron Lett. 1996, 3,7, 2197.
2. 2. Gronowitz, S.; Moses, P.; Hornfeldt, A.-B.; Hakansson, R. Ark. Kemi. 1961, 17, 165.
3. 3. (a) Daoust, G.; Leclerc, M. J. Macromolecules 1991, 24, 455.
4. (b) Coffey, M.; McKellar, B. R.; Reinhardt, B. A.; Nijakowski, T.; Felda, W. A. Synth. Commun. 1996, 26, 2205 and references cited therein.
5. (c) Leclerc, M.; Daoust, G.; J. Chem. Soc., Chem. Commun. 1990, 273.
6. 4. For representatives, see: (a) Sauter, F.; Stanetty, P.; Frohlich, H. Heterocycles 1987, 26, 2657.
7. (b) Shu, P.; Chiang, L.-Y. J. Chem. Soc., Chem. Commun. 1981, 920.
8. (c) Chiang, L.-Y.; Shu, P.; Holf, D. J. Org. Chem. 1983, 48, 4713.
9. (d) Reddinger, J. L.; Reynolds, J. R. J. Org. Chem. 1996, 61, 4833.
10. (e) Tamao, K.; Kodama, S.; Nakajima, I.; Kumada, M.; Minato, A.; Suzuki, K. Tetrahedron 1982, 38, 3347 and references cited therein.
11. 5. The formation of bis-organomanganese bromides can not 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.
12. 6. (a) Jen, K.-Y.; Miller, G. G.; Elsenbaumer, R. L. J. Chem. Soc., Chem. Commun. 1986, 1346.
13. (b) Hotta, S.; Rughooputh, S. D. D. V.; Heeger, A. J.; Wudl, F. Macromolecules 1987, 20, 212.
14. (c) Sato, M.; Tanaka, S.; Kaeriyama, K. J. Chem. Soc.,Chem. Commun. 1986, 873.
15. 7. (a) Hartman, G. D.; Halczenko, W.; Smith, R. L.; Sugrue, M. F.; Mallorga, P. J.; Michelson, S. R.; Randall, W. C.; Schwam, H.; Sondey, J. M. J. Med. Chem. 1992, 35, 3822.
16. (b) Holmes, J. M.; Lee, G. C. M.; Wijono, M.; Weinkam, R.; Wheeler, L. A.; Garst, M. E. J. Med. Chem. 1994, 37, 1646.
17. 8. (a) Gronowitz, S. and Hakansson, R. Arkiv. Kemi. 1959, 17, 73.
18. (b) Gronowitz, S. Organic Sulphur Chemistry - Structure, Mechanism, and Synthesis; Stering, C. J. M., Butterworths.1975, pp.203-228.
19. 9. (a) Zhang, Y.; Hornfeldt, A. -B.; Gronowitz, S. J. Heterocycl. Chem. 1995, 32, 435.
20. (b) Ritter, S. K.; Noftle, R. E. Chem. Mater. 1992, 4, 872.
21. (c) Arnswald, M.; Neumann, W. P. J. Org. Chem. 1993, 58, 7022.
22. (d) Yamamura, K.; Miyake, H.; Nakatsuji, S. Chem. Lett. 1992, 1213.
23. (e) Gronowitz, S. Arkiv. Kemi. 1958, 12, 533.
24. 10. Moses, P.; Gronowitz, S. Arkiv. Kemi. 1971, 18, 119.
25. 11. Wu, X.; Rieke, R. D. J. Org. Chem. 1995, 60, 6658.; This report from our laboratory has shown that the direct oxidative additions to 3-iodothiophene were completed by using Rieke magnesium (Mg*) and Rieke zinc (Zn*). However, 3-bromothiophene was unreactive toward Mg* and Zn*.
26. 12. In typical preparation, lithium (9.68 mmol), naphthalene (1.48 mmol), and anhydrous manganese iodide (4.71 mmol) under argon were stirred in freshly distilled THF (10 mL) for 1h at room temperature.
27. 13. The formation of bis-organomanganese bromides can not 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.
28. 14. 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.