Indium-mediated organometallic reactions in aqueous media: The nature of the allylindium intermediate [6]

Journal of the American Chemical Society

Volumn 121, Issue 13, 1999, Pages 3228-3229

  Chan, Tak Hang ^a   Yang, Yang ^a  

^a MCGILL UNIVERSITY   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; INDIUM; ORGANOMETALLIC COMPOUND;

CHEMICAL REACTION; CHEMICAL STRUCTURE; DIASTEREOISOMER; LETTER; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY;

EID: 0001310676     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja984359n     Document Type: Letter

References (44)

1. For some recent examples of indium-mediated reactions in organic solvents, see: (a) Araki, S.; Imsi, A.; Shimizu, K.; Yamada, M.; Mori, A.; Butsugan, Y. J. Org. Chem. 1995, 60, 1841. (b) Fujiwara, N.; Yamamoto, Y. J. Org. Chem. 1997, 62, 2318. Ranu, B. C.; Majee, A. Chem. Commun. 1997, 1225. Reetz, M. T.; Haning, H. J. Organomet. Chem. 1997, 541, 117. (e) For review, see Cintas, P. Synlett, 1995, 1087.
2. For some recent examples of indium-mediated reactions in organic solvents, see: (a) Araki, S.; Imsi, A.; Shimizu, K.; Yamada, M.; Mori, A.; Butsugan, Y. J. Org. Chem. 1995, 60, 1841. (b) Fujiwara, N.; Yamamoto, Y. J. Org. Chem. 1997, 62, 2318. Ranu, B. C.; Majee, A. Chem. Commun. 1997, 1225. Reetz, M. T.; Haning, H. J. Organomet. Chem. 1997, 541, 117. (e) For review, see Cintas, P. Synlett, 1995, 1087.
3. For some recent examples of indium-mediated reactions in organic solvents, see: (a) Araki, S.; Imsi, A.; Shimizu, K.; Yamada, M.; Mori, A.; Butsugan, Y. J. Org. Chem. 1995, 60, 1841. (b) Fujiwara, N.; Yamamoto, Y. J. Org. Chem. 1997, 62, 2318. Ranu, B. C.; Majee, A. Chem. Commun. 1997, 1225. Reetz, M. T.; Haning, H. J. Organomet. Chem. 1997, 541, 117. (e) For review, see Cintas, P. Synlett, 1995, 1087.
4. For some recent examples of indium-mediated reactions in organic solvents, see: (a) Araki, S.; Imsi, A.; Shimizu, K.; Yamada, M.; Mori, A.; Butsugan, Y. J. Org. Chem. 1995, 60, 1841. (b) Fujiwara, N.; Yamamoto, Y. J. Org. Chem. 1997, 62, 2318. Ranu, B. C.; Majee, A. Chem. Commun. 1997, 1225. Reetz, M. T.; Haning, H. J. Organomet. Chem. 1997, 541, 117. (e) For review, see Cintas, P. Synlett, 1995, 1087.
5. For some recent examples of indium-mediated reactions in organic solvents, see: (a) Araki, S.; Imsi, A.; Shimizu, K.; Yamada, M.; Mori, A.; Butsugan, Y. J. Org. Chem. 1995, 60, 1841. (b) Fujiwara, N.; Yamamoto, Y. J. Org. Chem. 1997, 62, 2318. Ranu, B. C.; Majee, A. Chem. Commun. 1997, 1225. Reetz, M. T.; Haning, H. J. Organomet. Chem. 1997, 541, 117. (e) For review, see Cintas, P. Synlett, 1995, 1087.
6. For some recent examples of In-mediated reactions in aqueous media, see: (a) Paquette, L. A.; Rothhaar, R. R.; Issac, M.; Rogers, L. M.; Rogers, R. D. J. Org. Chem. 1998, 63, 5463. (b) Chan, T. H.; Lu, W. Tetrahedron Lett. 1998, 39, 8605. Yi, X.-H.; Meng, Y.; Hua, X.-G.; Li, C. J. J. Org. Chem. 1998, 63, 7472 Loh, T.-P.; Cao, G.-Q.; Pei, J. Tetrahedron Lett. 1998, 39, 1453, 1457. (e) For review, see: Li, C. J.; Chan, T. H. Organic Reactions in Aqueous Media; John Wiley & Sons: New York, 1997.
7. For some recent examples of In-mediated reactions in aqueous media, see: (a) Paquette, L. A.; Rothhaar, R. R.; Issac, M.; Rogers, L. M.; Rogers, R. D. J. Org. Chem. 1998, 63, 5463. (b) Chan, T. H.; Lu, W. Tetrahedron Lett. 1998, 39, 8605. Yi, X.-H.; Meng, Y.; Hua, X.-G.; Li, C. J. J. Org. Chem. 1998, 63, 7472 Loh, T.-P.; Cao, G.-Q.; Pei, J. Tetrahedron Lett. 1998, 39, 1453, 1457. (e) For review, see: Li, C. J.; Chan, T. H. Organic Reactions in Aqueous Media; John Wiley & Sons: New York, 1997.
8. For some recent examples of In-mediated reactions in aqueous media, see: (a) Paquette, L. A.; Rothhaar, R. R.; Issac, M.; Rogers, L. M.; Rogers, R. D. J. Org. Chem. 1998, 63, 5463. (b) Chan, T. H.; Lu, W. Tetrahedron Lett. 1998, 39, 8605. Yi, X.-H.; Meng, Y.; Hua, X.-G.; Li, C. J. J. Org. Chem. 1998, 63, 7472 Loh, T.-P.; Cao, G.-Q.; Pei, J. Tetrahedron Lett. 1998, 39, 1453, 1457. (e) For review, see: Li, C. J.; Chan, T. H. Organic Reactions in Aqueous Media; John Wiley & Sons: New York, 1997.
9. For some recent examples of In-mediated reactions in aqueous media, see: (a) Paquette, L. A.; Rothhaar, R. R.; Issac, M.; Rogers, L. M.; Rogers, R. D. J. Org. Chem. 1998, 63, 5463. (b) Chan, T. H.; Lu, W. Tetrahedron Lett. 1998, 39, 8605. Yi, X.-H.; Meng, Y.; Hua, X.-G.; Li, C. J. J. Org. Chem. 1998, 63, 7472 Loh, T.-P.; Cao, G.-Q.; Pei, J. Tetrahedron Lett. 1998, 39, 1453, 1457. (e) For review, see: Li, C. J.; Chan, T. H. Organic Reactions in Aqueous Media; John Wiley & Sons: New York, 1997.
10. For some recent examples of In-mediated reactions in aqueous media, see: (a) Paquette, L. A.; Rothhaar, R. R.; Issac, M.; Rogers, L. M.; Rogers, R. D. J. Org. Chem. 1998, 63, 5463. (b) Chan, T. H.; Lu, W. Tetrahedron Lett. 1998, 39, 8605. Yi, X.-H.; Meng, Y.; Hua, X.-G.; Li, C. J. J. Org. Chem. 1998, 63, 7472 Loh, T.-P.; Cao, G.-Q.; Pei, J. Tetrahedron Lett. 1998, 39, 1453, 1457. (e) For review, see: Li, C. J.; Chan, T. H. Organic Reactions in Aqueous Media; John Wiley & Sons: New York, 1997.
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17. Paquette, L. A.; Lobben, P. C. J. Org. Chem. 1998, 63, 5604. and references therein.
18. For examples, see: (a) Chan, T. H.; Lee, M. C. J. Org. Chem. 1995, 60, 4228. (b) Gordon, D. M.; Whitesides, G. M. J. Org. Chem. 1993, 58, 7939. Chan, T. H.; Xin, Y.-C.; von Itzstein, M. J. Org. Chem. 1997, 62, 3500. Choi, S. K.; Lee, S.; Whiteside, G. M. J. Org. Chem. 1996, 61, 8739.
19. For examples, see: (a) Chan, T. H.; Lee, M. C. J. Org. Chem. 1995, 60, 4228. (b) Gordon, D. M.; Whitesides, G. M. J. Org. Chem. 1993, 58, 7939. Chan, T. H.; Xin, Y.-C.; von Itzstein, M. J. Org. Chem. 1997, 62, 3500. Choi, S. K.; Lee, S.; Whiteside, G. M. J. Org. Chem. 1996, 61, 8739.
20. For examples, see: (a) Chan, T. H.; Lee, M. C. J. Org. Chem. 1995, 60, 4228. (b) Gordon, D. M.; Whitesides, G. M. J. Org. Chem. 1993, 58, 7939. Chan, T. H.; Xin, Y.-C.; von Itzstein, M. J. Org. Chem. 1997, 62, 3500. Choi, S. K.; Lee, S.; Whiteside, G. M. J. Org. Chem. 1996, 61, 8739.
21. For examples, see: (a) Chan, T. H.; Lee, M. C. J. Org. Chem. 1995, 60, 4228. (b) Gordon, D. M.; Whitesides, G. M. J. Org. Chem. 1993, 58, 7939. Chan, T. H.; Xin, Y.-C.; von Itzstein, M. J. Org. Chem. 1997, 62, 3500. Choi, S. K.; Lee, S.; Whiteside, G. M. J. Org. Chem. 1996, 61, 8739.
22. Nesmeyanov, A. N.; Sokolik, R. A. The Organic Compounds of Boron, Alminum, Gallium, Indium and Thallium; North-Holland Publishing Company: Amsterdam, 1967.
23. Recently, allylation of aldehydes with magnesium in water has been observed. Both allylmagnesium intermediate and metal surface reaction have been proposed to account for the formation of products. See: Li, C.-J.; Zhang, W. C. J. Am. Chem. Soc. 1998, 120, 9102.
24. Kim, E.; Gordon, D. M.; Schmid, W.; Whitesides, G. M. J. Org. Chem. 1993, 58, 5500.
25. 7) which showed two sets of allyl signals at δ 1.75 (d, J = 8 Hz) and 2.02 (d, J = 8 Hz).
26. (a) Araki, S.; Shimizu, T.; Johar, P. S.; Jin, S.-J.; Butsugan, Y. J. Org. Chem. 1991, 56, 2538.
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31. (f) Capps, S. M.; Lloyd-Jones, G. C.; Murray, M.; Peakman, T. M.; Walsh, K. E. Tetrahedron Lett. 1998, 39, 2853.
32. The formation of allyl alcohol can be explained by the hydrolysis of allyl bromide under the Lewis acid influence of indium bromides formed in the reaction. This was verified by independent experiments.
33. Dennis, L. M.; Work, R. W.; Rochow, E. G. J. Am. Chem. Soc. 1934, 56, 1047.
34. Gilman, H.; Jones, R. G. J. Am. Chem. Soc. 1940, 62, 2353
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38. 1H NMR.
39. Although diallylmercury is unreactive towards ketones, it reacts with aldehydes in aqueous media to give the corresponding homoallylic alcohols. Chan, T. H.; Yang, Y., manuscript to be published.
40. 2.
41. 2O to give an allylmetal compound with an allylic signal at 2.8 ppm. We are in the process of deducing its structure. However, if an allylindium species were generated under such conditions, we demontrated that it was not able to allylate acetophenone and therefore it cannot be the reactive allylindium intermediate responsible for the allylation reaction.
42. While lower oxidation state inorganic compounds of indium are well-known, there are only a few examples of organoindium(I) compounds. They are all derivatives of cyclopentadienylindium. The parent compound was reported to be extremely sensitive to atmospheric oxygen but is stable to water. Fischer, E. O.; Hofmann, H. P. Angew Chem. 1957, 69, 639.
43. 2O at room temperature is more compatible with a π-bonded allylindium structure than a π-bonded structure or rapidly equilibrating allylic isomers.
44. 22