Preparation of highly functionalized Grignard reagents by an iodine-magnesium exchange reaction and its application in solid-phase synthesis

Angewandte Chemie - International Edition

Volumn 37, Issue 12, 1998, Pages 1701-1703

  Boymond, Laure ^b   Rottländer, Mario ^a   Cahiez, Gérard ^b   Knochel, Paul ^a  

^a PHILIPPS UNIVERSITY MARBURG   (Germany)

^b Ecole Superieure de Chimie Organique et Minerale   (France)

Author keywords

Copper; Grignard reactions; Iodine magnesium exchange; Magnesium; Solid phase synthesis

Indexed keywords

ARYL BROMIDE; BENZALDEHYDE; C ARYL IODIDE; GRIGNARD REAGENT; IMMOBILIZATION; IODINE; MAGNESIUM;

EID: 0039827338     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19980703)37:12<1701::AID-ANIE1701>3.0.CO;2-U     Document Type: Article

References (33)

1. Handbook of Grignard-Reagents (Eds.: G. S. Silverman, P. E. Rakita), Marcel Dekker, New York, 1996.
2. G. H. Posner, Org. React. 1975, 22, 253; B. H. Lipshutz, S. Sengupta, ibid. 1992, 41, 135; T.-Y. Luh, Acc. Chem. Res. 1991, 24, 257; K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374; R. J. P. Corriu, J. P. Masse, J. Chem. Soc. Chem. Commun. 1972, 144: T. Hayashi, M. Kumada, Acc. Chem. Res. 1982, 15, 395; E. Negishi, A. O. King, N. Okukado, J. Org. Chem. 1977, 42, 1821; M. T. Reetz, Top. Curr. Chem. 1982, 106; B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 31; M. T. Reetz, Angew. Chem. 1984, 96, 542; Angew. Chem. Int. Ed. Engl. 1984, 23, 556; G. Cahiez, S. Marquais, M. Alami, Org. Synth. 1993, 72, 135; G. Cahiez, B. Laboue, Tetrahedron Lett. 1992, 33, 4439.
3. G. H. Posner, Org. React. 1975, 22, 253; B. H. Lipshutz, S. Sengupta, ibid. 1992, 41, 135; T.-Y. Luh, Acc. Chem. Res. 1991, 24, 257; K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374; R. J. P. Corriu, J. P. Masse, J. Chem. Soc. Chem. Commun. 1972, 144: T. Hayashi, M. Kumada, Acc. Chem. Res. 1982, 15, 395; E. Negishi, A. O. King, N. Okukado, J. Org. Chem. 1977, 42, 1821; M. T. Reetz, Top. Curr. Chem. 1982, 106; B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 31; M. T. Reetz, Angew. Chem. 1984, 96, 542; Angew. Chem. Int. Ed. Engl. 1984, 23, 556; G. Cahiez, S. Marquais, M. Alami, Org. Synth. 1993, 72, 135; G. Cahiez, B. Laboue, Tetrahedron Lett. 1992, 33, 4439.
4. G. H. Posner, Org. React. 1975, 22, 253; B. H. Lipshutz, S. Sengupta, ibid. 1992, 41, 135; T.-Y. Luh, Acc. Chem. Res. 1991, 24, 257; K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374; R. J. P. Corriu, J. P. Masse, J. Chem. Soc. Chem. Commun. 1972, 144: T. Hayashi, M. Kumada, Acc. Chem. Res. 1982, 15, 395; E. Negishi, A. O. King, N. Okukado, J. Org. Chem. 1977, 42, 1821; M. T. Reetz, Top. Curr. Chem. 1982, 106; B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 31; M. T. Reetz, Angew. Chem. 1984, 96, 542; Angew. Chem. Int. Ed. Engl. 1984, 23, 556; G. Cahiez, S. Marquais, M. Alami, Org. Synth. 1993, 72, 135; G. Cahiez, B. Laboue, Tetrahedron Lett. 1992, 33, 4439.
5. G. H. Posner, Org. React. 1975, 22, 253; B. H. Lipshutz, S. Sengupta, ibid. 1992, 41, 135; T.-Y. Luh, Acc. Chem. Res. 1991, 24, 257; K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374; R. J. P. Corriu, J. P. Masse, J. Chem. Soc. Chem. Commun. 1972, 144: T. Hayashi, M. Kumada, Acc. Chem. Res. 1982, 15, 395; E. Negishi, A. O. King, N. Okukado, J. Org. Chem. 1977, 42, 1821; M. T. Reetz, Top. Curr. Chem. 1982, 106; B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 31; M. T. Reetz, Angew. Chem. 1984, 96, 542; Angew. Chem. Int. Ed. Engl. 1984, 23, 556; G. Cahiez, S. Marquais, M. Alami, Org. Synth. 1993, 72, 135; G. Cahiez, B. Laboue, Tetrahedron Lett. 1992, 33, 4439.
6. G. H. Posner, Org. React. 1975, 22, 253; B. H. Lipshutz, S. Sengupta, ibid. 1992, 41, 135; T.-Y. Luh, Acc. Chem. Res. 1991, 24, 257; K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374; R. J. P. Corriu, J. P. Masse, J. Chem. Soc. Chem. Commun. 1972, 144: T. Hayashi, M. Kumada, Acc. Chem. Res. 1982, 15, 395; E. Negishi, A. O. King, N. Okukado, J. Org. Chem. 1977, 42, 1821; M. T. Reetz, Top. Curr. Chem. 1982, 106; B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 31; M. T. Reetz, Angew. Chem. 1984, 96, 542; Angew. Chem. Int. Ed. Engl. 1984, 23, 556; G. Cahiez, S. Marquais, M. Alami, Org. Synth. 1993, 72, 135; G. Cahiez, B. Laboue, Tetrahedron Lett. 1992, 33, 4439.
7. G. H. Posner, Org. React. 1975, 22, 253; B. H. Lipshutz, S. Sengupta, ibid. 1992, 41, 135; T.-Y. Luh, Acc. Chem. Res. 1991, 24, 257; K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374; R. J. P. Corriu, J. P. Masse, J. Chem. Soc. Chem. Commun. 1972, 144: T. Hayashi, M. Kumada, Acc. Chem. Res. 1982, 15, 395; E. Negishi, A. O. King, N. Okukado, J. Org. Chem. 1977, 42, 1821; M. T. Reetz, Top. Curr. Chem. 1982, 106; B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 31; M. T. Reetz, Angew. Chem. 1984, 96, 542; Angew. Chem. Int. Ed. Engl. 1984, 23, 556; G. Cahiez, S. Marquais, M. Alami, Org. Synth. 1993, 72, 135; G. Cahiez, B. Laboue, Tetrahedron Lett. 1992, 33, 4439.
8. G. H. Posner, Org. React. 1975, 22, 253; B. H. Lipshutz, S. Sengupta, ibid. 1992, 41, 135; T.-Y. Luh, Acc. Chem. Res. 1991, 24, 257; K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374; R. J. P. Corriu, J. P. Masse, J. Chem. Soc. Chem. Commun. 1972, 144: T. Hayashi, M. Kumada, Acc. Chem. Res. 1982, 15, 395; E. Negishi, A. O. King, N. Okukado, J. Org. Chem. 1977, 42, 1821; M. T. Reetz, Top. Curr. Chem. 1982, 106; B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 31; M. T. Reetz, Angew. Chem. 1984, 96, 542; Angew. Chem. Int. Ed. Engl. 1984, 23, 556; G. Cahiez, S. Marquais, M. Alami, Org. Synth. 1993, 72, 135; G. Cahiez, B. Laboue, Tetrahedron Lett. 1992, 33, 4439.
9. G. H. Posner, Org. React. 1975, 22, 253; B. H. Lipshutz, S. Sengupta, ibid. 1992, 41, 135; T.-Y. Luh, Acc. Chem. Res. 1991, 24, 257; K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374; R. J. P. Corriu, J. P. Masse, J. Chem. Soc. Chem. Commun. 1972, 144: T. Hayashi, M. Kumada, Acc. Chem. Res. 1982, 15, 395; E. Negishi, A. O. King, N. Okukado, J. Org. Chem. 1977, 42, 1821; M. T. Reetz, Top. Curr. Chem. 1982, 106; B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 31; M. T. Reetz, Angew. Chem. 1984, 96, 542; Angew. Chem. Int. Ed. Engl. 1984, 23, 556; G. Cahiez, S. Marquais, M. Alami, Org. Synth. 1993, 72, 135; G. Cahiez, B. Laboue, Tetrahedron Lett. 1992, 33, 4439.
10. G. H. Posner, Org. React. 1975, 22, 253; B. H. Lipshutz, S. Sengupta, ibid. 1992, 41, 135; T.-Y. Luh, Acc. Chem. Res. 1991, 24, 257; K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374; R. J. P. Corriu, J. P. Masse, J. Chem. Soc. Chem. Commun. 1972, 144: T. Hayashi, M. Kumada, Acc. Chem. Res. 1982, 15, 395; E. Negishi, A. O. King, N. Okukado, J. Org. Chem. 1977, 42, 1821; M. T. Reetz, Top. Curr. Chem. 1982, 106; B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 31; M. T. Reetz, Angew. Chem. 1984, 96, 542; Angew. Chem. Int. Ed. Engl. 1984, 23, 556; G. Cahiez, S. Marquais, M. Alami, Org. Synth. 1993, 72, 135; G. Cahiez, B. Laboue, Tetrahedron Lett. 1992, 33, 4439.
11. G. H. Posner, Org. React. 1975, 22, 253; B. H. Lipshutz, S. Sengupta, ibid. 1992, 41, 135; T.-Y. Luh, Acc. Chem. Res. 1991, 24, 257; K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374; R. J. P. Corriu, J. P. Masse, J. Chem. Soc. Chem. Commun. 1972, 144: T. Hayashi, M. Kumada, Acc. Chem. Res. 1982, 15, 395; E. Negishi, A. O. King, N. Okukado, J. Org. Chem. 1977, 42, 1821; M. T. Reetz, Top. Curr. Chem. 1982, 106; B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 31; M. T. Reetz, Angew. Chem. 1984, 96, 542; Angew. Chem. Int. Ed. Engl. 1984, 23, 556; G. Cahiez, S. Marquais, M. Alami, Org. Synth. 1993, 72, 135; G. Cahiez, B. Laboue, Tetrahedron Lett. 1992, 33, 4439.
12. G. H. Posner, Org. React. 1975, 22, 253; B. H. Lipshutz, S. Sengupta, ibid. 1992, 41, 135; T.-Y. Luh, Acc. Chem. Res. 1991, 24, 257; K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374; R. J. P. Corriu, J. P. Masse, J. Chem. Soc. Chem. Commun. 1972, 144: T. Hayashi, M. Kumada, Acc. Chem. Res. 1982, 15, 395; E. Negishi, A. O. King, N. Okukado, J. Org. Chem. 1977, 42, 1821; M. T. Reetz, Top. Curr. Chem. 1982, 106; B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 31; M. T. Reetz, Angew. Chem. 1984, 96, 542; Angew. Chem. Int. Ed. Engl. 1984, 23, 556; G. Cahiez, S. Marquais, M. Alami, Org. Synth. 1993, 72, 135; G. Cahiez, B. Laboue, Tetrahedron Lett. 1992, 33, 4439.
13. G. H. Posner, Org. React. 1975, 22, 253; B. H. Lipshutz, S. Sengupta, ibid. 1992, 41, 135; T.-Y. Luh, Acc. Chem. Res. 1991, 24, 257; K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374; R. J. P. Corriu, J. P. Masse, J. Chem. Soc. Chem. Commun. 1972, 144: T. Hayashi, M. Kumada, Acc. Chem. Res. 1982, 15, 395; E. Negishi, A. O. King, N. Okukado, J. Org. Chem. 1977, 42, 1821; M. T. Reetz, Top. Curr. Chem. 1982, 106; B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 31; M. T. Reetz, Angew. Chem. 1984, 96, 542; Angew. Chem. Int. Ed. Engl. 1984, 23, 556; G. Cahiez, S. Marquais, M. Alami, Org. Synth. 1993, 72, 135; G. Cahiez, B. Laboue, Tetrahedron Lett. 1992, 33, 4439.
14. G. H. Posner, Org. React. 1975, 22, 253; B. H. Lipshutz, S. Sengupta, ibid. 1992, 41, 135; T.-Y. Luh, Acc. Chem. Res. 1991, 24, 257; K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374; R. J. P. Corriu, J. P. Masse, J. Chem. Soc. Chem. Commun. 1972, 144: T. Hayashi, M. Kumada, Acc. Chem. Res. 1982, 15, 395; E. Negishi, A. O. King, N. Okukado, J. Org. Chem. 1977, 42, 1821; M. T. Reetz, Top. Curr. Chem. 1982, 106; B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 31; M. T. Reetz, Angew. Chem. 1984, 96, 542; Angew. Chem. Int. Ed. Engl. 1984, 23, 556; G. Cahiez, S. Marquais, M. Alami, Org. Synth. 1993, 72, 135; G. Cahiez, B. Laboue, Tetrahedron Lett. 1992, 33, 4439.
15. G. H. Posner, Org. React. 1975, 22, 253; B. H. Lipshutz, S. Sengupta, ibid. 1992, 41, 135; T.-Y. Luh, Acc. Chem. Res. 1991, 24, 257; K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374; R. J. P. Corriu, J. P. Masse, J. Chem. Soc. Chem. Commun. 1972, 144: T. Hayashi, M. Kumada, Acc. Chem. Res. 1982, 15, 395; E. Negishi, A. O. King, N. Okukado, J. Org. Chem. 1977, 42, 1821; M. T. Reetz, Top. Curr. Chem. 1982, 106; B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 31; M. T. Reetz, Angew. Chem. 1984, 96, 542; Angew. Chem. Int. Ed. Engl. 1984, 23, 556; G. Cahiez, S. Marquais, M. Alami, Org. Synth. 1993, 72, 135; G. Cahiez, B. Laboue, Tetrahedron Lett. 1992, 33, 4439.
16. Examples of halogen-magnesium exchange reactions: J. Villiéras, Bull. Soc. Chim. Fr. 1967, 1520; H. H. Paradies, H. Görbing, Angew. Chem. 1969, 81, 293; Angew. Chem. Int. Ed. Engl. 1969, 8, 279. C. F. Smith, G. J. Moore, C. Tamborski, J. Organomet. Chem. 1971, 33, C21; G. Cahiez, D. Bernard, J. F. Normant. ibid. 1976, 113, 107; D. Seyferth, R. Lambert, ibid. 1973, 54, 123; N. Redwane, P. Moreau, A. Commeyras, J. Fluorine Chem. 1982, 20, 699; N. Furukawa, T. Shibutani, H. Fujihara, Tetrahedron Lett. 1987, 28, 5845; H. Nishiyama, K. Isaka, K. Itoh, K. Ohm, H. Nagase, K. Matsumoto, H. Yoshiwara, J. Org. Chem. 1992, 57, 407: C. Bolm, D. Pupowicz, Tetrahedron Lett. 1997, 38, 7349.
17. Examples of halogen-magnesium exchange reactions: J. Villiéras, Bull. Soc. Chim. Fr. 1967, 1520; H. H. Paradies, H. Görbing, Angew. Chem. 1969, 81, 293; Angew. Chem. Int. Ed. Engl. 1969, 8, 279. C. F. Smith, G. J. Moore, C. Tamborski, J. Organomet. Chem. 1971, 33, C21; G. Cahiez, D. Bernard, J. F. Normant. ibid. 1976, 113, 107; D. Seyferth, R. Lambert, ibid. 1973, 54, 123; N. Redwane, P. Moreau, A. Commeyras, J. Fluorine Chem. 1982, 20, 699; N. Furukawa, T. Shibutani, H. Fujihara, Tetrahedron Lett. 1987, 28, 5845; H. Nishiyama, K. Isaka, K. Itoh, K. Ohm, H. Nagase, K. Matsumoto, H. Yoshiwara, J. Org. Chem. 1992, 57, 407: C. Bolm, D. Pupowicz, Tetrahedron Lett. 1997, 38, 7349.
18. Examples of halogen-magnesium exchange reactions: J. Villiéras, Bull. Soc. Chim. Fr. 1967, 1520; H. H. Paradies, H. Görbing, Angew. Chem. 1969, 81, 293; Angew. Chem. Int. Ed. Engl. 1969, 8, 279. C. F. Smith, G. J. Moore, C. Tamborski, J. Organomet. Chem. 1971, 33, C21; G. Cahiez, D. Bernard, J. F. Normant. ibid. 1976, 113, 107; D. Seyferth, R. Lambert, ibid. 1973, 54, 123; N. Redwane, P. Moreau, A. Commeyras, J. Fluorine Chem. 1982, 20, 699; N. Furukawa, T. Shibutani, H. Fujihara, Tetrahedron Lett. 1987, 28, 5845; H. Nishiyama, K. Isaka, K. Itoh, K. Ohm, H. Nagase, K. Matsumoto, H. Yoshiwara, J. Org. Chem. 1992, 57, 407: C. Bolm, D. Pupowicz, Tetrahedron Lett. 1997, 38, 7349.
19. Examples of halogen-magnesium exchange reactions: J. Villiéras, Bull. Soc. Chim. Fr. 1967, 1520; H. H. Paradies, H. Görbing, Angew. Chem. 1969, 81, 293; Angew. Chem. Int. Ed. Engl. 1969, 8, 279. C. F. Smith, G. J. Moore, C. Tamborski, J. Organomet. Chem. 1971, 33, C21; G. Cahiez, D. Bernard, J. F. Normant. ibid. 1976, 113, 107; D. Seyferth, R. Lambert, ibid. 1973, 54, 123; N. Redwane, P. Moreau, A. Commeyras, J. Fluorine Chem. 1982, 20, 699; N. Furukawa, T. Shibutani, H. Fujihara, Tetrahedron Lett. 1987, 28, 5845; H. Nishiyama, K. Isaka, K. Itoh, K. Ohm, H. Nagase, K. Matsumoto, H. Yoshiwara, J. Org. Chem. 1992, 57, 407: C. Bolm, D. Pupowicz, Tetrahedron Lett. 1997, 38, 7349.
20. Examples of halogen-magnesium exchange reactions: J. Villiéras, Bull. Soc. Chim. Fr. 1967, 1520; H. H. Paradies, H. Görbing, Angew. Chem. 1969, 81, 293; Angew. Chem. Int. Ed. Engl. 1969, 8, 279. C. F. Smith, G. J. Moore, C. Tamborski, J. Organomet. Chem. 1971, 33, C21; G. Cahiez, D. Bernard, J. F. Normant. ibid. 1976, 113, 107; D. Seyferth, R. Lambert, ibid. 1973, 54, 123; N. Redwane, P. Moreau, A. Commeyras, J. Fluorine Chem. 1982, 20, 699; N. Furukawa, T. Shibutani, H. Fujihara, Tetrahedron Lett. 1987, 28, 5845; H. Nishiyama, K. Isaka, K. Itoh, K. Ohm, H. Nagase, K. Matsumoto, H. Yoshiwara, J. Org. Chem. 1992, 57, 407: C. Bolm, D. Pupowicz, Tetrahedron Lett. 1997, 38, 7349.
21. Examples of halogen-magnesium exchange reactions: J. Villiéras, Bull. Soc. Chim. Fr. 1967, 1520; H. H. Paradies, H. Görbing, Angew. Chem. 1969, 81, 293; Angew. Chem. Int. Ed. Engl. 1969, 8, 279. C. F. Smith, G. J. Moore, C. Tamborski, J. Organomet. Chem. 1971, 33, C21; G. Cahiez, D. Bernard, J. F. Normant. ibid. 1976, 113, 107; D. Seyferth, R. Lambert, ibid. 1973, 54, 123; N. Redwane, P. Moreau, A. Commeyras, J. Fluorine Chem. 1982, 20, 699; N. Furukawa, T. Shibutani, H. Fujihara, Tetrahedron Lett. 1987, 28, 5845; H. Nishiyama, K. Isaka, K. Itoh, K. Ohm, H. Nagase, K. Matsumoto, H. Yoshiwara, J. Org. Chem. 1992, 57, 407: C. Bolm, D. Pupowicz, Tetrahedron Lett. 1997, 38, 7349.
22. Examples of halogen-magnesium exchange reactions: J. Villiéras, Bull. Soc. Chim. Fr. 1967, 1520; H. H. Paradies, H. Görbing, Angew. Chem. 1969, 81, 293; Angew. Chem. Int. Ed. Engl. 1969, 8, 279. C. F. Smith, G. J. Moore, C. Tamborski, J. Organomet. Chem. 1971, 33, C21; G. Cahiez, D. Bernard, J. F. Normant. ibid. 1976, 113, 107; D. Seyferth, R. Lambert, ibid. 1973, 54, 123; N. Redwane, P. Moreau, A. Commeyras, J. Fluorine Chem. 1982, 20, 699; N. Furukawa, T. Shibutani, H. Fujihara, Tetrahedron Lett. 1987, 28, 5845; H. Nishiyama, K. Isaka, K. Itoh, K. Ohm, H. Nagase, K. Matsumoto, H. Yoshiwara, J. Org. Chem. 1992, 57, 407: C. Bolm, D. Pupowicz, Tetrahedron Lett. 1997, 38, 7349.
23. Examples of halogen-magnesium exchange reactions: J. Villiéras, Bull. Soc. Chim. Fr. 1967, 1520; H. H. Paradies, H. Görbing, Angew. Chem. 1969, 81, 293; Angew. Chem. Int. Ed. Engl. 1969, 8, 279. C. F. Smith, G. J. Moore, C. Tamborski, J. Organomet. Chem. 1971, 33, C21; G. Cahiez, D. Bernard, J. F. Normant. ibid. 1976, 113, 107; D. Seyferth, R. Lambert, ibid. 1973, 54, 123; N. Redwane, P. Moreau, A. Commeyras, J. Fluorine Chem. 1982, 20, 699; N. Furukawa, T. Shibutani, H. Fujihara, Tetrahedron Lett. 1987, 28, 5845; H. Nishiyama, K. Isaka, K. Itoh, K. Ohm, H. Nagase, K. Matsumoto, H. Yoshiwara, J. Org. Chem. 1992, 57, 407: C. Bolm, D. Pupowicz, Tetrahedron Lett. 1997, 38, 7349.
24. Examples of halogen-magnesium exchange reactions: J. Villiéras, Bull. Soc. Chim. Fr. 1967, 1520; H. H. Paradies, H. Görbing, Angew. Chem. 1969, 81, 293; Angew. Chem. Int. Ed. Engl. 1969, 8, 279. C. F. Smith, G. J. Moore, C. Tamborski, J. Organomet. Chem. 1971, 33, C21; G. Cahiez, D. Bernard, J. F. Normant. ibid. 1976, 113, 107; D. Seyferth, R. Lambert, ibid. 1973, 54, 123; N. Redwane, P. Moreau, A. Commeyras, J. Fluorine Chem. 1982, 20, 699; N. Furukawa, T. Shibutani, H. Fujihara, Tetrahedron Lett. 1987, 28, 5845; H. Nishiyama, K. Isaka, K. Itoh, K. Ohm, H. Nagase, K. Matsumoto, H. Yoshiwara, J. Org. Chem. 1992, 57, 407: C. Bolm, D. Pupowicz, Tetrahedron Lett. 1997, 38, 7349.
25. Examples of halogen-magnesium exchange reactions: J. Villiéras, Bull. Soc. Chim. Fr. 1967, 1520; H. H. Paradies, H. Görbing, Angew. Chem. 1969, 81, 293; Angew. Chem. Int. Ed. Engl. 1969, 8, 279. C. F. Smith, G. J. Moore, C. Tamborski, J. Organomet. Chem. 1971, 33, C21; G. Cahiez, D. Bernard, J. F. Normant. ibid. 1976, 113, 107; D. Seyferth, R. Lambert, ibid. 1973, 54, 123; N. Redwane, P. Moreau, A. Commeyras, J. Fluorine Chem. 1982, 20, 699; N. Furukawa, T. Shibutani, H. Fujihara, Tetrahedron Lett. 1987, 28, 5845; H. Nishiyama, K. Isaka, K. Itoh, K. Ohm, H. Nagase, K. Matsumoto, H. Yoshiwara, J. Org. Chem. 1992, 57, 407: C. Bolm, D. Pupowicz, Tetrahedron Lett. 1997, 38, 7349.
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33. A patent covering the preparation of polyfunctional Grignard reagents has been submitted.