Metalated Nitriles: Halogen - Metal Exchange with α-Halonitriles

Organic Letters

Volumn 6, Issue 4, 2004, Pages 501-503

  Fleming, Fraser F ^a   Zhang, Zhiyu ^a   Knochel, Paul ^b  

^a DUQUESNE UNIVERSITY   (United States)

^b UNIVERSITY OF MUNICH   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; BROMINE DERIVATIVE; CHLORINE DERIVATIVE; CYANIDE; HALOGEN; KETONE; LITHIUM DERIVATIVE; MAGNESIUM DERIVATIVE; METAL; NITRILE; ORGANOMETALLIC COMPOUND; REAGENT;

ALKYLATION; ARTICLE; CONFORMATION; GRIGNARD REACTION; METHYLATION; STEREOCHEMISTRY;

EID: 1342332931     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol036202s     Document Type: Article

References (38)

1. (a) Fleming, F. F.; Shook, B. C. Tetrahedron 2002, 58, 1.
2. (b) Arseniyadis, S.; Kyler, K. S.; Watt, D. S. Org. React. 1984, 31, 1.
3. Fatiadi, A. J. In The Chemistry of Triple-Bonded Functional Groups. Supplement C; Patai, S., Rappoport, Z., Eds.; Wiley: New York, 1983; pp 1157-1190.
4. Boche, G. Angew. Chem., Int. Ed. 1989, 28, 277.
5. Zarges, W.; Marsch, M.; Harms, K.; Boche, G. Angew. Chem., Int. Ed. 1989, 28, 1392.
6. For leading references, see: (a) Corset, J.; Castellà-Ventura, M. ; Froment, F.; Strzalko, T.; Wartski, L. J. Org. Chem. 2003, 68, 3902. (b) Carlier, P. R.; Lo, C. W.-S. J. Am. Chem. Soc. 2000, 122, 12819. (c) Carlier, P. R.; Lucht, B. L.; Collum, D. B. J. Am. Chem. Soc. 1994, 116, 11602.
7. For leading references, see: (a) Corset, J.; Castellà-Ventura, M. ; Froment, F.; Strzalko, T.; Wartski, L. J. Org. Chem. 2003, 68, 3902. (b) Carlier, P. R.; Lo, C. W.-S. J. Am. Chem. Soc. 2000, 122, 12819. (c) Carlier, P. R.; Lucht, B. L.; Collum, D. B. J. Am. Chem. Soc. 1994, 116, 11602.
8. For leading references, see: (a) Corset, J.; Castellà-Ventura, M. ; Froment, F.; Strzalko, T.; Wartski, L. J. Org. Chem. 2003, 68, 3902. (b) Carlier, P. R.; Lo, C. W.-S. J. Am. Chem. Soc. 2000, 122, 12819. (c) Carlier, P. R.; Lucht, B. L.; Collum, D. B. J. Am. Chem. Soc. 1994, 116, 11602.
9. (a) For a crystal structure, see: Boche, G.; Harms, K.; Marsch, M. J. Am. Chem. Soc. 1988, 110, 6925. (b) For solution alkylations, see: Walborsky, H. M.; Motes, J. M. J. Am. Chem. Soc. 1970, 92, 2445.
10. (a) For a crystal structure, see: Boche, G.; Harms, K.; Marsch, M. J. Am. Chem. Soc. 1988, 110, 6925. (b) For solution alkylations, see: Walborsky, H. M.; Motes, J. M. J. Am. Chem. Soc. 1970, 92, 2445.
11. Fleming, F. F.; Shook, B. C. J. Org. Chem. 2002, 67, 2885.
12. Carlier, P. R. Chirality 2003, 15, 340.
13. For recent examples, see: (a) Fleming, F. F.; Gudipati, V.; Steward, O. W. J. Org. Chem. 2003, 68, 3943. (b) Bunlaksananusorn, T.; Rodriguez, A. L.; Knochel, P. Chem. Commun. 2001, 745. (c) Makosza, M.; Judka, M. Chem. Eur. J. 2002, 8, 4234.
14. For recent examples, see: (a) Fleming, F. F.; Gudipati, V.; Steward, O. W. J. Org. Chem. 2003, 68, 3943. (b) Bunlaksananusorn, T.; Rodriguez, A. L.; Knochel, P. Chem. Commun. 2001, 745. (c) Makosza, M.; Judka, M. Chem. Eur. J. 2002, 8, 4234.
15. For recent examples, see: (a) Fleming, F. F.; Gudipati, V.; Steward, O. W. J. Org. Chem. 2003, 68, 3943. (b) Bunlaksananusorn, T.; Rodriguez, A. L.; Knochel, P. Chem. Commun. 2001, 745. (c) Makosza, M.; Judka, M. Chem. Eur. J. 2002, 8, 4234.
16. Fleming, F. F.; Funk, L. A.; Altundas, R.; Sharief, V. J. Org. Chem. 2002, 67, 9414.
17. Boudier, A.; Bromm, L. O.; Lotz, M.; Knochel, P. Angew. Chem., Int. Ed. 2000, 39, 4415.
18. (a) William, A. D.; Kobayashi, Y. J. Org. Chem. 2002, 67, 8771.
19. (b) Aoki, Y.; Oshima, K.; Utimoto, K. Chem. Lett. 1995, 463.
20. (a) Hartzler, H. D. In The Chemistry of the Cyano Group; Rappoport, Z., Ed.; Wiley-Interscience: New York, 1970; Chapter 11, pp 671-716.
21. (b) For a novel photochemical conjugate addition-halogenation, see: Mitani, M.; Kato, I.; Koyama, K. J. Am. Chem. Soc. 1983, 105, 6719.
22. (a) Aggarwal, V. K.; Ali, A.; Coogan, M. P. Tetrahedron 1999, 55, 293.
23. (b) Ranganathan, S.; Ranganathan, D.; Mehrota, A. K. Synthesis 1977, 289.
24. (a) Russel, G. A.; Shi, B. Z. Synlett 1993, 701.
25. (b) Giese, B.; González-Gómez, J.-A. Chem. Ber. 1986, 119, 1291.
26. Stevens, C. L.; Coffield, T. H. J. Am. Chem. Soc. 1951, 73, 103.
27. Freeman, P. K.; Balls, D. M. Brown, D. J. J. Org. Chem. 1968, 33, 2211.
28. Rouz-Schmitt, M.-C.; Petit, A.; Sevin, A.; Seyden-Penne, J.; Anh, N. T. Tetrahedron 1990, 46, 1263.
29. For an excellent survey of halogen-metal exchange reactions in the presence of electrophiles, see: Clayden, J. In Organolithiums: Selectivity for Synthesis; Pergamon: Amsterdam, 2002; pp 116 and 284-287.
30. 13C NMR.
31. Only a trace of the iodo alcohol arising from the deprotonation of 4e and addition of the resulting anion to cyclohexenone was detected.
32. Reference 19, Chapter 3.
33. Halogen-metal exchange through an ate complex leads to C-metalation, although progression to an N-metalated nitrile is conceivable: (a) Hoffmann, R. W.; Brönstrup, M.; Müller, M. Org. Lett. 2003, 5, 313. (b) Schulze, V.; Brönstrup, M.; Böhm, V. P. W.; Schwerdtfeger, P.; Schimeczek, M.; Hoffmann, R. W. Angew. Chem., Int. Ed. 1998, 37, 824. (c) Reich, H. J.; Green, D. P.; Phillips, N. H.; Borst, J. P.; Reich, I. L. Phosphorus, Sulfur, Silicon 1992, 67, 83.
34. Halogen-metal exchange through an ate complex leads to C-metalation, although progression to an N-metalated nitrile is conceivable: (a) Hoffmann, R. W.; Brönstrup, M.; Müller, M. Org. Lett. 2003, 5, 313. (b) Schulze, V.; Brönstrup, M.; Böhm, V. P. W.; Schwerdtfeger, P.; Schimeczek, M.; Hoffmann, R. W. Angew. Chem., Int. Ed. 1998, 37, 824. (c) Reich, H. J.; Green, D. P.; Phillips, N. H.; Borst, J. P.; Reich, I. L. Phosphorus, Sulfur, Silicon 1992, 67, 83.
35. Halogen-metal exchange through an ate complex leads to C-metalation, although progression to an N-metalated nitrile is conceivable: (a) Hoffmann, R. W.; Brönstrup, M.; Müller, M. Org. Lett. 2003, 5, 313. (b) Schulze, V.; Brönstrup, M.; Böhm, V. P. W.; Schwerdtfeger, P.; Schimeczek, M.; Hoffmann, R. W. Angew. Chem., Int. Ed. 1998, 37, 824. (c) Reich, H. J.; Green, D. P.; Phillips, N. H.; Borst, J. P.; Reich, I. L. Phosphorus, Sulfur, Silicon 1992, 67, 83.
36. A 2:1 ratio of diastereomers was employed.
37. 1H NMR analysis of the crude reaction mixture failed to identify any of the independently prepared diastereomeric nitrile.
38. Basu, A.; Thayumanavan, S. Angew. Chem., Int. Ed. 2002, 41, 717.