Metalated nitriles: Organolithium, -magnesium? and -copper exchange of α-halonitriles

Journal of Organic Chemistry

Volumn 70, Issue 6, 2005, Pages 2200-2205

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

^a DUQUESNE UNIVERSITY   (United States)

^b UNIVERSITY OF MUNICH   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDES; HALOGEN COMPOUNDS; METALLIZING; ORGANOMETALLICS; REACTION KINETICS;

Α-HALONITRILES; ALKYLLITHIUM; GRIGNARD REAGENTS; HALOGEN-METAL EXCHANGE;

CYANIDES;

ALDEHYDE DERIVATIVE; COPPER; COPPER DERIVATIVE; HALOGEN; LITHIUM DERIVATIVE; MAGNESIUM; MAGNESIUM DERIVATIVE; METAL; NITRILE; ORGANOLITHIUM COMPOUND;

ALKYLATION; ARTICLE; CHEMICAL REACTION; CORRELATION ANALYSIS; GRIGNARD REACTION; LITHIATION;

COPPER; HYDROCARBONS, HALOGENATED; LITHIUM; MAGNESIUM; MOLECULAR CONFORMATION; NITRILES; ORGANOMETALLIC COMPOUNDS; STEREOISOMERISM;

EID: 15444369069     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo047877r     Document Type: Article

References (105)

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. Nitriles are powerful inductive stabilizing groups with weak delocalizing effects: (a) Richard, J. P.; Williams, G.; Gao, J. J. Am. Chem. Soc. 1999, 121, 715. (b) Bradamante, S.; Pagani, G. A. J. Chem. Soc., Perkin Trans. 2 1986, 1035. (c) Dayal, S. K.; Ehrenson, S.; Taft, R. W. J. Am. Chem. Soc. 1972, 94, 9113.
4. Nitriles are powerful inductive stabilizing groups with weak delocalizing effects: (a) Richard, J. P.; Williams, G.; Gao, J. J. Am. Chem. Soc. 1999, 121, 715. (b) Bradamante, S.; Pagani, G. A. J. Chem. Soc., Perkin Trans. 2 1986, 1035. (c) Dayal, S. K.; Ehrenson, S.; Taft, R. W. J. Am. Chem. Soc. 1972, 94, 9113.
5. Nitriles are powerful inductive stabilizing groups with weak delocalizing effects: (a) Richard, J. P.; Williams, G.; Gao, J. J. Am. Chem. Soc. 1999, 121, 715. (b) Bradamante, S.; Pagani, G. A. J. Chem. Soc., Perkin Trans. 2 1986, 1035. (c) Dayal, S. K.; Ehrenson, S.; Taft, R. W. J. Am. Chem. Soc. 1972, 94, 9113.
6. (a) Enders, D.; Kirchhoff, J.; Gerdes, P.; Mannes, D.; Raabe, G.; Runsink, J.; Boche, G.; Marsch, M.; Ahlbrecht, H.; Sommer, H. Eur. J. Org. Chem. 1998, 63.
7. (b) Kawakami, Y.; Hisada, H.; Yamashita, Y. Tetrahedron Lett. 1985, 26, 5835.
8. (c) Watt, D. S. Synth. Commun. 1974, 4, 127.
9. (d) Kruger, C. R.; Rochow, E. G. Angew. Chem., Int. Ed. 1963, 2, 617.
10. (e) Prober, M. J. Am. Chem. Soc. 1956, 78, 2274.
11. Eliel, E. L.; Wilen, S. H.; Mander, L. N. In Stereochemistry of Organic Compounds; Wiley: New York, 1994; pp 696-7.
12. Fleming, F. F.; Zhang, Z. Tetrahedron 2005, 61, 747.
13. 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.
14. (a) Koch, R.; Wiedel, B.; Anders, E. J. Org. Chem. 1996, 61, 2523.
15. (b) For the related deprotonation of cyclopropanecarbonitrile see: Carlier, P. R. Chirality 2003, 15, 340.
16. Boche, G. Angew. Chem., Int. Ed. 1989, 28, 277.
17. 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.
18. 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.
19. 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.
20. Le Questel, J.-Y.; Berthelot, M.; Laurence C. J. Phys. Org. Chem. 2000, 13, 347. The bond length is the mean of CN distance obtained from 5059 nitriles in the Cambridge Structural Database.
21. Zarges, W.; Marsch, M.; Harms, K.; Boche, G. Angew. Chem., Int. Ed. 1989, 28, 1392.
22. (a) Reference 8.
23. (b) For stereoinduction with ephedrine ligands see: Carlier, P. R.; Lam, W. W.-F.; Wan, N. C.; Williams, I. D. Angew. Chem., Int. Ed. 1998, 37, 2252.
24. Sott, R.; Granander, J.; Hilmersson, G. J. Am. Chem. Soc. 2004, 126, 6798.
25. Walborsky, H. M.; Motes, J. M. J. Am. Chem. Soc. 1970, 92, 2445.
26. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
27. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
28. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
29. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
30. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
31. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
32. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
33. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
34. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
35. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
36. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
37. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
38. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
39. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
40. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
41. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
42. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
43. Subsequent approaches to chiral metalated nitriles have employed noncovalently linked chiral additives: (a) Suto, Y.; Kumagai, N.; Matsunaga, S.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 3147. (b) Reference 12b. (c) Kuwano, R.; Miyazaki, H.; Ito, Y. Chem. Commun. 1998, 71. (d) Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. (e) Soai, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1979, 52, 3371. For metalated nitriles containing chiral auxiliaries see: (f) Enders, D.; Shilvock, J. P.; Raabe, G. J. Chem. Soc., Perkin Trans. I 1999, 1617. (g) Roux, M.-C.; Patel, S.; Mérienne, C.; Morgant, G.; Wartski, L. Bull. Chem. Soc. Fr. 1997, 134, 809. (h) Schrader, T. Chem. Eur. J. 1997, 3, 1273. (i) Enders, D.; Kirchhoff, J.; Lausberg, V. Liebigs. Ann. 1996, 1361. (j) Roux, M.-C.; Wartski, L.; Nierlich, M.; Lance, M. Tetrahedron 1996, 52, 10083. (k) Enders, D.; Kirchhoff, J.; Mannes, D.; Raabe, G. Synthesis 1995, 659. (l) Cativiela, C.; Díaz-de-Villegas, M. D.; Gálvez, J. A.; Lapeña, Y. Tetrahedron 1995, 51, 5921. (m) Cativiela, C.; Dĩaz-de-Villegas, M. D.; Gãlvez, J. A. J. Org. Chem. 1994, 59, 2497. (n) Enders, D.; Mannes, D.; Raabe, G. Synlett 1992, 837. (o) Enders, D.; Gerdes, P.; Kipphardt, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 179. (p) Hanamoto, T.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 2463. (q) Marco, J. L.; Royer, J.; Husson, H.-P. Tetrahedron Lett. 1985, 26, 3567. (r) Enders, D.; Lotter, H.; Maigrot, N.; Mazaleyrat, J.-P.; Welvart, Z. Nouv. J. Chem. 1984, 8, 747.
44. Hoz, S.; Aurbach, D. J. Am. Chem. Soc. 1980, 102, 2340.
45. The only X-ray structure of a C-lithiated nitrile is for an N-and C-lithiated cyclopropanecarbonitrile dimer: Boche, G.; Harms, K.; Marsch, M. J. Am. Chem. Soc. 1988, 110, 6925.
46. (a) Alburquerque, P. R.; Pinhas, A. R.; Krause Bauer, J. A. Inorg. Chim. Acta 2000, 298, 239.
47. (b) Ragaini, F.; Porta, F.; Fumagalli, A.; Demartin, F. Organometallics 1991, 10, 3785.
48. (c) Porta, F.; Ragaini, F.; Cenini, S.; Demartin, F. Organometallics 1990, 9, 929.
49. (d) Cowan, R. L.; Trogler, W. J. Am. Chem. Soc. 1989, 111, 4750.
50. (e) Del Pra, A.; Forsellini, E.; Bombieri, G.; Michelin, R. A.; Ros, R. J. Chem. Soc., Dalton Trans. 1979, 1862.
51. (f) Lenarda, M.; Pahor, N. B.; Calligaris, M.; Graziani, M.; Randaccio, L. J. Chem. Soc., Chem. Commun. 1978, 279.
52. (g) Schlodder, R.; Ibers, J. A.; Lenarda, M.; Graziani, M. J. Am. Chem. Soc. 1974, 96, 6893.
53. (a) Thibonnet, J.; Vu, V. A.; Berillon, L.; Knochel, P. Tetrahedron 2002, 58, 4787.
54. (b) Thibonnet, J.; Knochel, P. Tetrahedron Lett. 2000, 41, 3319.
55. (a) Orsini, F. Synthesis 1985, 500.
56. See also: (b) Goasdoue, N.; Gaudemar, M. J. Organomet. Chem. 1972, 39, 17.
57. (a) Naota, T.; Tannna, A.; Murahashi, S.-I. Chem. Commun. 2001, 63.
58. (b) Naota, T.; Tannna, A.; Murahashi, S.-I. J. Am. Chem. Soc. 2000, 122, 2960. For an analogous interconversion of palladium complexes see: Kujime, M.; Hikichi, S.; Akita, M. Organometallics 2001, 20, 4049.
59. (b) Naota, T.; Tannna, A.; Murahashi, S.-I. J. Am. Chem. Soc. 2000, 122, 2960. For an analogous interconversion of palladium complexes see: Kujime, M.; Hikichi, S.; Akita, M. Organometallics 2001, 20, 4049.
60. Fleming, F. F.; Shook, B. C. J. Org. Chem. 2002, 67, 2885.
61. Trost, B. M.; Florez, J.; Jebaratnam, D. J. J. Am. Chem. Soc. 1987, 109, 613.
62. (a) Caron, S.; Vazquez, E.; Wojcik, J. M. J. Am. Chem. Soc. 2000, 122, 712.
63. (b) Leung, C.-S.; Rowlands, M. G.; Jarman, M.; Foster, A. B.; Griggs, L. J.; Wilman, D. E. V. J. Med. Chem. 1987, 30, 1550.
64. For a preliminary communication see: Fleming, F. F.; Zhang, Z.; Knochel, P. Org. Lett. 2004, 6, 501.
65. Knochel, P.; Dohle, W.; Gommermarm, N.; Kneisel, F. F.; Kopp, F.; Korn, T.; Sapountzis, I.; Vu, V. A. Angew. Chem., Int. Ed. 2003, 42, 4303.
66. For related metal-halogen exchanges with α-iodoketones see: (a) William, A. D.; Kobayashi, Y. J. Org. Chem. 2002, 67, 8771. (b) Aoki, Y.; Oshima, K.; Utimoto, K. Chem. Lett. 1995, 463.
67. For related metal-halogen exchanges with α-iodoketones see: (a) William, A. D.; Kobayashi, Y. J. Org. Chem. 2002, 67, 8771. (b) Aoki, Y.; Oshima, K.; Utimoto, K. Chem. Lett. 1995, 463.
68. Banwell, M. G.; Clark, G. R.; Hockless, D. C. R.; Pallich, S. Aust. J. Chem. 2001, 54, 691.
69. Monti, S. A.; Chen, S.-C.; Yang, Y.-L.; Yuan, S.-S.; Bourgeois, O. P. J. Org. Chem. 1978, 43, 4062.
70. Clayden, J. In Organolithiums: Selectivity for Synthesis; Pergamon: Amsterdam, The Netherlands, 2002; Chapter 3.
71. Stevens, C. L.; Coffield, T. H. J. Am. Chem. Soc. 1951, 73, 103.
72. Freeman, P. K.; Balls, D. M.; Brown, D. J. J. Org. Chem. 1968, 33, 2211.
73. (a) Russel, G. A.; Shi, B. Z. Synlett 1993, 701.
74. (b) Giese, B.; González-Gómez, J.-A. Chem. Ber. 1986, 119, 1291.
75. (c) Giese, B.; Antonio, J.; Gómez, G. Tetrahedron Lett. 1982, 23, 2765.
76. For reviews see: (a) Reference 5. (b) Aggarwal, V. K.; Ali, A.; Coogan, M. P. Tetrahedron 1999, 55, 293. (c) Ranganathan, S.; Ranganathan, D.; Mehrota, A. K. Synthesis 1977, 289.
77. For reviews see: (a) Reference 5. (b) Aggarwal, V. K.; Ali, A.; Coogan, M. P. Tetrahedron 1999, 55, 293. (c) Ranganathan, S.; Ranganathan, D.; Mehrota, A. K. Synthesis 1977, 289.
78. For reviews see: (a) Reference 5. (b) Aggarwal, V. K.; Ali, A.; Coogan, M. P. Tetrahedron 1999, 55, 293. (c) Ranganathan, S.; Ranganathan, D.; Mehrota, A. K. Synthesis 1977, 289.
79. (a) Hoffmann, R. W.; Brönstrup, M.; Muller, M. Org. Lett. 2003, 5, 313.
80. (b) Schulze, V.; Brönstrup, M.; Böhm, V. P. W.; Schwerdtfeger, P.; Schimeczek, M.; Hoffmann, R. W. Angew. Chem., Int. Ed. 1998, 37, 824.
81. (c) Reich, H. J.; Green, D. P.; Phillips, N. H.; Borst, J. P.; Reich, I. L. Phosphorus, Sulfur, Silicon 1992, 67, 83.
82. For an excellent survey of halogen-metal exchange reactions in the presence of electrophiles see: ref 30, pp 116 and 284-287.
83. (a) Werry, J.; Stamm, H.; Sommer, A. Chem. Ber. 1990, 123, 1553.
84. (b) Šindelá, K.; Holubek, J.; Svátek, E.; Schlanger, J.; Dlabač, A.; Valchář, M.; Hurbantová, M.; Protiva, M. Collect. Czech. Chem. Commun. 1990, 55, 782.
85. (c) Chauffaille, J.; Hebert, E.; Welvart, Z. J. Chem. Soc., Perkin Trans. 2 1982, 1645.
86. (d) Seux, R.; Morel, G.; Foucaud, A. Tetrahedron 1975, 31, 1335.
87. Only a trace of the iodo alcohol arising from the deprotonation of 12c and addition of the resulting anion to cyclohexenone was detected.
88. Rouz-Schmitt, M.-C.; Petit, A.; Sevin, A.; Seyden-Penne, J.; Anh, N. T. Tetrahedron 1990, 46, 1263.
89. (a) Yang, X.; Rotter, T.; Piazza, C.; Knochel, P. Org. Lett. 2003, 5, 1229.
90. (b) Piazza, C.; Knochel, P. Angew. Chem., Int. Ed. 2002, 41, 3263.
91. 2CuLi see: Posner, G. H.; Switzer, C. J. Am. Chem. Soc. 1986, 108, 1239. For a related exchange with a trifluorosulfonyl ester see: Petit, Y.; Sanner, C.; Larchevêque, M. Tetrahedron Lett. 1990, 31, 2149.
92. 2CuLi see: Posner, G. H.; Switzer, C. J. Am. Chem. Soc. 1986, 108, 1239. For a related exchange with a trifluorosulfonyl ester see: Petit, Y.; Sanner, C.; Larchevêque, M. Tetrahedron Lett. 1990, 31, 2149.
93. For excellent regioselectivity analyses see: (a) Yamanaka, M.; Kato, S.; Nakamura, E. J. Am. Chem. Soc. 2004, 126, 6287. (b) Breit, B.; Demel, P. In Modern Organocopper Chemistry; Krause, N., Ed.; Wiley-VCH: Weinheim, Germany, 2002; pp 188-223.
94. For excellent regioselectivity analyses see: (a) Yamanaka, M.; Kato, S.; Nakamura, E. J. Am. Chem. Soc. 2004, 126, 6287. (b) Breit, B.; Demel, P. In Modern Organocopper Chemistry; Krause, N., Ed.; Wiley-VCH: Weinheim, Germany, 2002; pp 188-223.
95. Obtained as a mixture of dl and meso isomers
96. For the synthesis of C-cuprated nitriles see: (a) Kondo, J.; Ito, Y.; Shinokubo, H.; Oshima, K. Angew. Chem., Int. Ed. 2004, 43, 106. (b) Tsuda, T.; Nakatsuka, T.; Hirayama, T.; Saegusa, T. J. Chem. Soc., Chem. Commun. 1974, 557. (c) Corey, E. J.; Kuwajima, I. Tetrahedron Lett. 1972, 487.
97. For the synthesis of C-cuprated nitriles see: (a) Kondo, J.; Ito, Y.; Shinokubo, H.; Oshima, K. Angew. Chem., Int. Ed. 2004, 43, 106. (b) Tsuda, T.; Nakatsuka, T.; Hirayama, T.; Saegusa, T. J. Chem. Soc., Chem. Commun. 1974, 557. (c) Corey, E. J.; Kuwajima, I. Tetrahedron Lett. 1972, 487.
98. For the synthesis of C-cuprated nitriles see: (a) Kondo, J.; Ito, Y.; Shinokubo, H.; Oshima, K. Angew. Chem., Int. Ed. 2004, 43, 106. (b) Tsuda, T.; Nakatsuka, T.; Hirayama, T.; Saegusa, T. J. Chem. Soc., Chem. Commun. 1974, 557. (c) Corey, E. J.; Kuwajima, I. Tetrahedron Lett. 1972, 487.
99. Aryl- and α-aminomethyl cuprates couple in the presence of electrophiles: (a) Dieter, R. K.; Li, S. J.; Chen, N. J. Org. Chem. 2004, 69, 2867. (b) Kronenburg, C. M. P.; Amijs, C. H. M.; Wijkens, P.; Jastrzebski, J. T. B. H.; van Koten, G. Tetrahedron Lett. 2002, 43, 1113. (c) Lipshutz, B. H.; Kayser, F.; Liu, Z.-P. Angew. Chem., Int. Ed. Engl. 1994, 33, 1842. (d) Lipshutz, B. H.; Siegmann, K.; Garcia, E. J. Am. Chem. Soc. 1991, 113, 8161.
100. Aryl- and α-aminomethyl cuprates couple in the presence of electrophiles: (a) Dieter, R. K.; Li, S. J.; Chen, N. J. Org. Chem. 2004, 69, 2867. (b) Kronenburg, C. M. P.; Amijs, C. H. M.; Wijkens, P.; Jastrzebski, J. T. B. H.; van Koten, G. Tetrahedron Lett. 2002, 43, 1113. (c) Lipshutz, B. H.; Kayser, F.; Liu, Z.-P. Angew. Chem., Int. Ed. Engl. 1994, 33, 1842. (d) Lipshutz, B. H.; Siegmann, K.; Garcia, E. J. Am. Chem. Soc. 1991, 113, 8161.
101. Aryl- and α-aminomethyl cuprates couple in the presence of electrophiles: (a) Dieter, R. K.; Li, S. J.; Chen, N. J. Org. Chem. 2004, 69, 2867. (b) Kronenburg, C. M. P.; Amijs, C. H. M.; Wijkens, P.; Jastrzebski, J. T. B. H.; van Koten, G. Tetrahedron Lett. 2002, 43, 1113. (c) Lipshutz, B. H.; Kayser, F.; Liu, Z.-P. Angew. Chem., Int. Ed. Engl. 1994, 33, 1842. (d) Lipshutz, B. H.; Siegmann, K.; Garcia, E. J. Am. Chem. Soc. 1991, 113, 8161.
102. Aryl- and α-aminomethyl cuprates couple in the presence of electrophiles: (a) Dieter, R. K.; Li, S. J.; Chen, N. J. Org. Chem. 2004, 69, 2867. (b) Kronenburg, C. M. P.; Amijs, C. H. M.; Wijkens, P.; Jastrzebski, J. T. B. H.; van Koten, G. Tetrahedron Lett. 2002, 43, 1113. (c) Lipshutz, B. H.; Kayser, F.; Liu, Z.-P. Angew. Chem., Int. Ed. Engl. 1994, 33, 1842. (d) Lipshutz, B. H.; Siegmann, K.; Garcia, E. J. Am. Chem. Soc. 1991, 113, 8161.
103. MeCu does not cause bromine-copper exchange with 12b.
104. The absence of 17 requires that no alkylation occurs between the organocopper and organocuprate 18a, with the bromomethane generated from fragmentation of the bromate 13a.
105. Potentially, the transition state for reductive elimination could arise from either an N- or C-cuprated nitrile ground state.