A convenient catalytic procedure for the addition of trimethylsilyl cyanide to functionalised ketones, mediated by InBr3 - Insight into the reaction mechanism

European Journal of Organic Chemistry

Volumn , Issue 19, 2002, Pages 3243-3249

  Bandini, Marco ^a   Cozzi, Pier Giorgio ^a   Garelli, Andrea ^a   Melchiorre, Paolo ^a   Umani Ronchi, Achille ^a  

^a UNIVERSITY OF BOLOGNA   (Italy)

Author keywords

Catalysis; Cyanides; Indium; Ketones; Kinetics

Indexed keywords

ALIPHATIC KETONE; AROMATIC COMPOUND; CYANIDE; CYANOHYDRIN; INDIUM; INDIUM BROMIDE; KETONE DERIVATIVE; SILANE DERIVATIVE; TRIMETHYLSILYL DERIVATIVE; TRIMETHYLSILYLCYANIDE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; SPECTROSCOPY;

EID: 0036794024     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/1099-0690(200210)2002:19<3243::AID-EJOC3243>3.0.CO;2-E     Document Type: Article

References (60)

1. R. J. H. Gregory, Chem. Rev. 1999, 99, 3649-3682.
2. A. Fujii, S. Sakaguchi, Y. Ishii, J. Org. Chem. 2000, 65, 6209-6212, and references cited therein.
3. S. Matsubara, T. Takai, K. Utimoto, Chem. Lett. 1991, 1447-1450.
4. [4a] Y. Yang, D. Wang, Synlett 1997, 861-868.
5. Y. Yang, D. Wang, Synlett 1997, 1379-1380.
6. P. Saravanan, R. V. Anand, V. R. Singh, Tetrahedron Lett. 1998, 39, 3823-3824.
7. P. G. Gassman, J. J. Talley, Tetrahedron Lett. 1978, 19, 3773-3776.
8. W. J. Greenlee, D. G. Hangauer, Tetrahedron Lett. 1983, 24, 4559-4560.
9. G. Jenner, Tetrahedron Lett. 1999, 40, 491-494.
10. J. K. Whitesell, R. Apodaca, Tetrahedron Lett. 1996, 37, 2525-2528.
11. M. Curini, F. Epifanio, M. C. Marcotullio, O. Rosati, M. Rossi, Synlett 1999, 315-316.
12. [11a] Diels-Alder reaction: T.-P. Loh, J. Pei, M. Lin, Chem. Commun. 1996, 2315-2316.
13. Aldol reaction: T.-P. Loh, J. Pei, G.-Q. Cao, Chem. Commun. 1996, 1819-1820. S. Kobayashi, T. Busujima, S. Nagayama, Tetrahedron Lett. 1998, 39, 1579-1582; T.-P. Loh, L.-L. Wei, Tetrahedron Lett. 1998, 39, 323-326.
14. Aldol reaction: T.-P. Loh, J. Pei, G.-Q. Cao, Chem. Commun. 1996, 1819-1820. S. Kobayashi, T. Busujima, S. Nagayama, Tetrahedron Lett. 1998, 39, 1579-1582; T.-P. Loh, L.-L. Wei, Tetrahedron Lett. 1998, 39, 323-326.
15. Aldol reaction: T.-P. Loh, J. Pei, G.-Q. Cao, Chem. Commun. 1996, 1819-1820. S. Kobayashi, T. Busujima, S. Nagayama, Tetrahedron Lett. 1998, 39, 1579-1582; T.-P. Loh, L.-L. Wei, Tetrahedron Lett. 1998, 39, 323-326.
16. Friedel-Crafts reaction: J. S. Yadav, S. Abraham, B. V. S. Reddy, G. Sabitha, Synthesis 2001, 2165-2168.
17. Aziridiation: S. Sengupta, S. Mondal, Tetrahedron Lett. 2000, 41, 6245-6248.
18. Allylation reaction: T. Miyai, K. Inoue, M. Yasuda, A. Baba, Synlett 1997, 699-700.
19. Biginelli reaction: B. C. Ranu, A. Hajra, U. Jana, J. Org. Chem. 2000, 65, 6270-6272.
20. Azidolysis of epoxycarboxylic acids: F. Fringuelli, F. Pizzo, L. Vaccaro, J. Org. Chem. 2001, 66, 3554-3558.
21. Y. Onishi, T. Ito, M. Yasuda, A. Baba, Eur. J. Org. Chem. 2002, 1578-1581.
22. Sakurai reaction: P. H. Lee, K. Lee, S. Sung, S. Chang, J. Org. Chem. 2001, 66, 8646-8649. K. Inoue, A. Sawada, I. Shibata, A. Baba, J. Am. Chem. Soc. 2002, 124, 906-907.
23. Sakurai reaction: P. H. Lee, K. Lee, S. Sung, S. Chang, J. Org. Chem. 2001, 66, 8646-8649. K. Inoue, A. Sawada, I. Shibata, A. Baba, J. Am. Chem. Soc. 2002, 124, 906-907.
24. [12a] Dithioacetalization: M. A. Ceschi, L. de Araujo Felix, C. Peppe, Tetrahedron Lett. 2000, 41, 9695-9699.
25. Tandem nucleophilic addition: M. Bandini, P. G. Cozzi, M. Giacomini, P. Melchiorre, S. Selva, A. Umani-Ronchi, J. Org. Chem. 2002, 67, 3700-3704.
26. Michael addition: M. Bandini, P. Melchiorre, A. Melloni, A. Umani-Ronchi, Synlett 2002, 1110-1114.
27. Stereoselective ring-opening of epoxides: M. Bandini, P. G. Cozzi, P. Melchiorre, A. Umani-Ronchi, J. Org. Chem., 2002, 67, 5386-5389.
28. [13a] Rearrangement of homoallylic alcohols: T.-P. Loh, K.-T. Tan, Q.-Y. Hu, Angew. Chem. Int. Ed. 2001, 40, 2921-2922.
29. Cyclization: T.-P. Loh, Q.-Y. Hu, K.-T. Tan, H.-S. Cheng, Org. Lett. 2001, 3, 2669-2672.
30. Synthesis of tetrahydrofurans: T.-P. Loh, Q.-Y. Hu, L.-T. Ma, J. Am. Chem. Soc. 2001, 123, 2450-2451.
31. [14a] B. C. Ranu, Eur. J. Org. Chem. 2000, 2347-2356.
32. K. K. Chauhan, C. G. Frost, J. Chem. Soc., Perkin Trans. 1 2000, 3015-3019.
33. G. Babu, P. T. Perumal, Aldrichimica Acta 2000, 33, 16-22.
34. M. Bandini, P. G. Cozzi, P. Melchiorre, A. Umani-Ronchi, Tetrahedron Lett. 2001, 42, 3041-3043.
35. 3 has already been studied as a catalyst (30 mol%) in the cyanation of aldehyde compounds in water (see: T.-P. Loh, K.-C. Xu, D. S.-C. Ho, K.-Y. Sim, Synlett 1998, 369-370); aliphatic and aromatic ketones did not undergo cyanation with TMSCN in this catalytic procedure, however.
36. For a recent example of catalytic cyanation of ketones by LiOR, see: H. S. Wilkinson, P. T. Grover, C. P. Vandenbossche, R. P. Bakale, N. N. Bhongle, S. A. Wald, C. H. Senanayake, Org. Lett. 2001, 3, 553-556.
37. V. I. Cohen, R. E. Gibson, L. H. Fen, R. De la Cruz, M. S. Gitter, E. Harimen, R. C. Rebe, J. Med. Chem. 1991, 34, 2989-2993.
38. A. E. Vougioukas, H. B. Kagan, Tetrahedron Lett. 1987, 28, 5513-5516.
39. When tributyltin cyanide was used as the cyano source, 2 was obtained in lower yield (62%).
40. 3 10 mol%)
41. L. H. Foley, J. Org. Chem. 1985, 50, 5204-5209.
42. R. Martin, P. Romea, C. Tey, F. Urpí, J. Vilarrasa, Synlett 1997, 1414-1415.
43. D. Russowsky, R. Z. Petersen, M. N. Godoi, R. A. Pilli, Tetrahedron Lett. 2000, 41, 9939-9942.
44. 1H NMR analysis of the crude mixture. The higher reaction rate of 21 in comparison with 25 is explained in terms of a reduction in the transition state energy associated with preformation of the indium/25 complex. The more selective substrate is therefore the more reactive.
45. The capability of the indium(III) species to bind multidentate substrates persists even in aqueous media, see:[25a] L. A. Paquette, T. M. Mitzel, J. Am. Chem. Soc. 1996, 118, 1931-1937.
46. T.-P. Loh, K.-Y. Sim, S.-C. Ho Diana, Synlett 1996, 263-264.
47. T.-P. Loh, X.-R. Li, Angew. Chem. Int. Ed. Engl. 1997, 36, 980-982.
48. L. A. Paquette, R. R. Rothhaar, J. Org. Chem. 1999, 64, 217-224.
49. 3 salt with PhCOMe has been isolated and characterised; see: S. Jin, V. McKee, M. Nieuwenhuyzen, W. T. Robinson, C. J. Wilkins, J. Chem. Soc., Dalton Trans. 1993, 3111-3116.
50. For an elegant discussion and interpretation of fractional reaction orders in catalytic enantioselective cyanation reactions, see: Y. N. Belokon', B. Green, N. S. Ikinnikov, V. S. Larichev, B. V. Lokshin, M. A. Moscalenko, M. North, C. Orizu, A. S. Peregudov, G. I. Timofeeva, Eur. J. Org. Chem. 2000, 2655-2661.
51. [28a] O. T. Beachley Jr., R. N. Rusinko, Inorg. Chem. 1979, 18, 1966-1968.
52. D. G. Tuck, in: Comprehensive Coordination Chemistry, vol. 3 (Ed.: G. Wilkinson), 1987, pp. 153-176 and references cited therein. All our attempts to obtain suitable crystals for an X-ray analysis were unsuccessful.
53. This result does not rule out the existence of a dimeric adduct; in fact, it is possible that the active dimeric species is an equilibrium intermediate present in a low concentration below the sensitivity of the NMR measurement.
54. For experimental evidence of transmetallation reactions between indium(III) salts and tetraalkyltin compounds, see ref.[15] and; J. Cossy, C. Rasamison, D. G. Pardo, J. A. Marshall, Synlett 2001, 629-633.
55. M. S. Samples, C. H. Yoder, J. Organomet. Chem. 1986, 312, 149-153.
56. No transmetallation reaction was observed even under forcing experimental conditions with an excess of TMSCN.
57. Although it has been clearly documented that trimethylsilyl cyanide and isocyanide exist in labile equilibrium in solution (normalliso ≈ 90: 10), no evidence of the active isocyanide form was observed in our spectroscopic investigations: [33a] M. R. Booth, S. G. Frankiss, Spectrochim. Acta 1970, 26A, 859-869.
58. J. A. Seckar, J. S. Thayer, Inorg. Chem. 1976, 15, 501-504.
59. [34a] M. A. Aswell, R. F. W. Jackson, Synthesis 1988, 229-231.
60. G. Zhu, A. L. Casalnuovo, X. Zhang, J. Org. Chem. 1998, 63, 8100-8101.