Indium-catalyzed reduction of allyl bromide with gallium or aluminum. Formation of allylgallium and allylaluminum sesquibromides

Organic Letters

Volumn 4, Issue 10, 2002, Pages 1727-1729

  Takai, Kazuhiko ^a   Ikawa, Yoshito ^a  

^a OKAYAMA UNIVERSITY   (Japan)

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EID: 0000168812     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol025784v     Document Type: Article

References (39)

1. For reviews of activated metals in organic synthesis, see: (a) Rieke, R. D. Top. Curr. Chem. 1975, 59, 1. Rieke, R. D. Aldrichimica Acta 2000, 33, 52.
2. For reviews of activated metals in organic synthesis, see: (a) Rieke, R. D. Top. Curr. Chem. 1975, 59, 1. Rieke, R. D. Aldrichimica Acta 2000, 33, 52.
3. (b) Fürstner, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 164.
4. (c) Cintas, P. Activated Metals in Organic Synthesis; CRC Press: Boca Raton, 1993.
5. (d) Fürstner, A. Active Metals: Preparation, Characterization, Application; VCH: Weinheim, 1996.
6. (a) Li-Na: Kamienski, C. W.; Esmay, D. L. J. Org. Chem. 1960, 25, 1807. Smith, W. N., Jr. J. Organomet. Chem. 1974, 82, 1.
7. (a) Li-Na: Kamienski, C. W.; Esmay, D. L. J. Org. Chem. 1960, 25, 1807. Smith, W. N., Jr. J. Organomet. Chem. 1974, 82, 1.
8. (b) Zn-Cu: Shank, R. S.; Shechter, H. J. Org. Chem. 1959, 24, 1825. LeGoff, E. J. Org. Chem. 1964, 29, 2048.
9. (b) Zn-Cu: Shank, R. S.; Shechter, H. J. Org. Chem. 1959, 24, 1825. LeGoff, E. J. Org. Chem. 1964, 29, 2048.
10. (c) Mn-Pb: Takai, K.; Ueda, T.; Hayashi, T.; Moriwake, T. Tetrahedron Lett. 1996, 37, 7049.
11. (a) Araki, S.; Ito, H.; Butsugan, Y. Appl. Organomet. Chem. 1988, 2, 475.
12. (b) Han, Y.; Huang, Y.-Z. Tetrahedron Lett. 1994, 35, 9433.
13. (c) Yamaguchi, M.; Sotokawa, T.; Hirama, M. Chem. Commun. 1997, 743.
14. (d) Araki, S.; Horie, T.; Kato, M.; Hirashita, T.; Yamamura, H.; Kawai, M. Tetrahedron Lett. 1999, 40, 2331.
15. (e) Usugi, S.-i.; Yorimitsu, H.; Oshima, K. Tetrahedron Lett. 2001, 42, 4535.
16. (f) Takai, K.; Ikawa, Y.; Ishii, K.; Kumanda, M. Chem. Lett. 2002, 172.
17. 2: Tanaka, H.; Yamashita, S.; Hamatani, T.; Ikemoto, Y.; Torii, S. Synth. Commun. 1987, 17, 789.
18. (b) Tanaka, H.; Nakahata, S.; Watanabe, H.; Zhao, J.; Kuroboshi, M.; Torii, S. Inorg. Chim. Acta 1999, 296, 204.
19. 3: Araki, S.; Jin, S.-J.; Idou, Y.; Butsugan, Y. Bull. Chem. Soc. Jpn. 1992, 65, 1736.
20. 0 is -0.3382 V; see: CRC Handbook of Chemistry and Physics, 82nd ed.; CRC Press: Boca Raton, 2001; p 8-21.
21. Zhang, X.-L.; Han, Y.; Tao, W.-T.; Huang, Y.-Z. J. Chem. Soc., Perkin Trans. 1 1995, 189.
22. (a) Araki, S.; Shimizu, T.; Johar, P. S.; Jin, S.-J.; Butsugan, Y. J. Org. Chem. 1991, 56, 2538.
23. (b) Araki, S.; Ito, H.; Butsugan, Y. J. Org. Chem. 1988, 53, 1831.
24. 3f Thus, a preparative method for a solution of allylgallium sesquibromide in THF is required.
25. 2 or KI-LiCl on gallium were not observed at 25°C in our experiments.
26. The melting point of gallium lowered to 15.3°C when 21.4 wt % of indium was added.
27. Gallium powder (99.9% purity, particle size ca. 0.85 mm diameter), shot (99.99%, ca. 1 g), and indium powder (99% purity, particle size ca. 75 μm diameter) were purchased from Kojundo Chemical Lab Co., Ltd.
28. When a shot of gallium(0) was used, the metal dissolved in 24 h.
29. A standard solution of allylgallium in THF (ca. 1.0 M solution, allyl bromide excess) was prepared as follows. A catalytic amount of indium powder (0.90 mmol) was added to a mixture of allyl bromide (30 mmol) and gallium metal (shot, 18 mmol) in THF (28 mL), and the mixture was stirred at 10°C for 24 h. When gallium powder was used, all of the gallium dissolved at 10°C within 2 h. The solution of allylgallium in THF could be stored at 5°C (in a refrigerator) for 1 month without decreasing the reactivity, but the reactivity decreased gradually at 25°C. An allylgallium solution without contamination of allyl bromide could be prepared by using an excess amount of gallium metal; however, the reactivity of this solution decreased faster at 25°C than that of the solution containing an excess amount of allyl bromide, and the solution became viscose.
30. A solution of allyl gallium in DME or DMF could also be prepared in the same fashion.
31. Addition of 3 to 3-phenylpropanal in THF occurred at 10°C in 30 min; however, the yield of 1-phenyl-5-hexen-1-ol (4) was 74% as a result of the formation of the corresponding ketone derived by Oppenauer-type oxidation in 7% yield and the diallylation product in 5% yield. See ref 4b. Formation of these byproducts was suppressed by addition of DMF (1.0 equiv of the gallium metal) in the reaction mixture, and 4 was obtained in 93% yield.
32. 8 solution. The supernatant solution was used for the NMR measurement.
33. 2: Araki, S.; Ito, H.; Katsumura, N.; Butsugan, Y. J. Organomet. Chem. 1989, 369, 291. Allylindium(I); Chan, T. H.; Yang, Y. J. Am. Chem. Soc. 1999, 121, 3228.
34. 2: Araki, S.; Ito, H.; Katsumura, N.; Butsugan, Y. J. Organomet. Chem. 1989, 369, 291. Allylindium(I); Chan, T. H.; Yang, Y. J. Am. Chem. Soc. 1999, 121, 3228.
35. Gallium(III) tribromide is soluble in the ethereal solvents to some extent.
36. -1. See: CRC Handbook of Chemistry and Physics, 82nd ed.; CRC Press: Boca Raton, 2001; p 9-51.
37. -1. See: CRC Handbook of Chemistry and Physics, 82nd ed.; CRC Press: Boca Raton, 2001; p 9-51.
38. 8. Allylic protons appeared at δ 1.90 ppm.
39. Barbier-type allylation of carbonyl compounds with allyl bromide and indium(I) regenerated on an aluminum sacrifical anode in THF was reported quite recently. Although the authors think indium(I) plays an important role in the reaction, they do not eliminate the possibility of the aluminum species for the allylation. Hilt, G.; Smolko, K. I. Angew. Chem., Int. Ed. 2001, 40, 3399.