A catalytic version of a nickel promoted intramolecular tandem cyclization-cyanation process

Tetrahedron Letters

Volumn 40, Issue 5, 1999, Pages 1057-1060

  Hinojosa, Susana ^a   Delgado, Antonio ^b   Llebaria, Amadeu ^a,b  

^a DEPARTMENT OF ENVIRONMENTAL CHEMISTRY   (Spain)

^b UNIVERSITY OF BARCELONA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; CYANIDE; NICKEL;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; CYCLIZATION; LIGAND BINDING; SYNTHESIS;

EID: 0033613681     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)80111-7     Document Type: Article

References (17)

1. a) Solé, D.; Cancho, Y.; Llebaria, A.; Moretó, J. M.; Delgado, A. J. Am. Chem. Soc. 1994, 116, 12133-12134.
2. b) Solé, D.: Cancho, Y.; Llebaria, A.; Moretó, J. M.; Delgado, A. J. Org. Chem. 1996, 61, 5895-5904.
3. c) Cancho, Y.; Martín, J.M.: Martínez, M.; Llebaria, A.; Moretó, J. M.; Delgado, A. Tetrahedron 1998, 54, 1221-1232.
4. Prepared by transcyanation of the corresponding chlorotrialkylsilane with TMSCN according to: Becu, C.; Anteunis, M.J.O. Bull. Soc. Chim. Belg. 1987, 96, 115-117.
5. Although reactions at 0°C led to major formation of cyclic vs. linear adducts, low product conversions were always found. On the other hand, by heating to 40°C, no improvement of the cyclic vs. linear ratio was observed in comparison with room temperature experiments.
6. For related Pd(0) carbocyanation of unsaturated bonds incapable of hydrogen beta-elimination see: a) Torii, S.; Okumoto, H.; Ozaki, H.; Nakayasu, S.; Tadokoro, T.; Kotani, T. Tetrahedron Lett. 1988, 23, 3499-3502.
7. b) Grigg, R.; Santhakumar, S.; Sridharan, V. Tetrahedron Lett. 1993, 34, 3163-3164.
8. For a Ni(0) catalyzed cyanation of vinyl halides see: Sakakibara, Y.; Enami, H.; Ogawa, H.; Fujimoto, S.; Kato, H.; Kunitake, K.; Sasaki, K.; Sakai, M. Bull. Chem. Soc. Jpn. 1995, 68, 3137-3143.
9. 13CNMR spectra.
10. Participation of a trialkylisonitrile, arising from a cyanide-isonitrile tautomerism, as a ligand in the catalytic process cannot be ruled out. For a Ni(0) catalyzed trialkylisonitrile insertion process see: Zhang, M.; Buchwald, S. L. J. Org. Chem., 1996. 61. 4498-4499.
11. For metal-catalyzed silyl-cyanation of triple bonds see: Suginome, M.; Kinugasa, H.; Ito, Y. Tetrahedron Lett. 1994, 35, 8635-8638. Chatani, N.; Takeyasu, T.; Horiuchi, N.; Hanafusa, T. J. Org. Chem., 1988, 53, 3539-3548.
12. For metal-catalyzed silyl-cyanation of triple bonds see: Suginome, M.; Kinugasa, H.; Ito, Y. Tetrahedron Lett. 1994, 35, 8635-8638. Chatani, N.; Takeyasu, T.; Horiuchi, N.; Hanafusa, T. J. Org. Chem., 1988, 53, 3539-3548.
13. In some instances, prolonged reaction times led to decomposition of the catalytic system, as evidenced by precipitation of insoluble material from the reaction mixture.
14. Reductive elimination on alkylcyanonickel compounds to give nitriles has been extensively studied in relation to the mechanism of nickel catalyzed hydrocyanation of olefins. See: a) Casalnuovo, A.L.; RajanBabu, T.V.; Ayers, T.A.; Warren, T.H. J. Am. Chem. Soc. 1994, 116, 9869-9882.
15. b) Tolman, C.A.; McKinney, R.J.; Seidel, W.C.; Druliner, J.D.; Stevens, W.R. Adv. Catal., 1985, 33, 1-46 and references therein.
16. 1-L6 (0.15 equiv) and silyl cyanides (1.25 equiv) (see Figure 1). In general, reactions in the presence of TESCN were faster than those with TMSCN under otherwise identical conditions.
17. In our previous stoichiometric one-pot tandem cyclization-quenching process, 3c was obtained as a complex diastereomeric mixture (see ref. 1).