The Mechanism of the Silver-Catalyzed Reaction of Grignard Reagents with Alkyl Halides

Journal of the American Chemical Society

Volumn 93, Issue 6, 1971, Pages 1483-1485

  Tamura, M ^a   Kochi, J ^a  

^a INDIANA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000676096     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00735a028     Document Type: Letter

References (29)

1. M. S. Kharasch and O. Reinmuth, “Grignard Reactions of Non-metallic Substances,” Prentice-Hall, Englewood Cliffs, N. J., 1954, p 122.
2. M. H. Abraham and M. J. Hogarth, J. Organometal. Chem., 12, 1, 497(1968);
3. D. I. Davies, J. N. Done, and D. H. Hey, J. Chem. Soc. C, 1392, 2021, 2506 (1969);
4. W. B. Smith, J. Org. Chem., 26, 4206 (1961);
5. L. H. Slaugh, J. Amer. Chem. Soc, 83, 2734 (1961);
6. G. Costa, G. Mestroni, and G. Boscarato, Ric. Sci., 7, 315 (1964);
7. R. O. C. Norman and W. A. Walters, J. Chem. Soc., 950 (1957).
8. Cf. J. H. Gardner, et al., J. Amer. Chem. Soc, 51, 3375 (1929); 59, 2583 (1937); 61, 2551 (1939);
9. J. Org. Chem., 5, 61, 126 (1940);
10. cf. also C. E. H. Bawn, et al, J. Chem. Soc, 3923 (1960);
11. F. Glocking and D. Kinston, J. Chem. Soc, 3001 (1959);
12. and H. C. Brown, et al., J. Amer. Chem. Soc, 83, 1001, 1002 (1961).
13. Hereafter solvation by THF will not be explicitly included.
14. Organometals are generally more stable in THF than in diethyl ether.
15. K. Wada, M. Tamura, and J. K. Kochi, J. Amer. Chem. Soc, 92, 6656 (1970).
16. This silver complex contained no silver(I) extractable with concentrated ammonia. It reacted with dilute aqueous sulfuric acid to precipitate silver metal quantitatively, but liberated no alkane in the process. It was capable of oxidatively dimerizing allyl and benzyl bromides quantitatively to biallyl and bibenzyl, respectively (silver bromide was formed), (b) We will refer hereafter to this as a soluble silver complex, although repeated and various attempts to isolate a pure compound have not yet been successful; compare, e.g., R. R. DeWald, J. M. Brooks, and M. A. Trickey, Chem. Commun., 963 (1970), and
17. R. S. Eachus and M. C. R. Symons, Chem. Commun., 1336 (1970).
18. Fluoroalkylsilver(I) species have been recently identified: W. T. Miller, et al., J. Amer. Chem. Soc, 90, 7367 (1968); 91, 6532 (1969);
19. V. R. Polishchuk, et al., Tetrahedron Lett., 3933 (1970);
20. see also, C. D. M. Beverwijk, et al., Organometal. Chem. Rev., 5, 215 (1970).
21. cannot be excluded at this point [cf. J. Kochi and P. J. Krusic, J. Amer. Chem. Soc., 91, 3940, 3942 (1969)].
22. Initiation of vinyl polymerization by silver powder and aralkyl halides has been shown [M. Kinoshita and N. Yoshizumi, J. Chem. Soc. Jap., 71, 409, 892 (1968)];
23. J. K. Kochi and J. W. Powers, J. Amer. Chem. Soc, 92, 137 (1970);
24. P. B. Chock and J. Halpern, J. Amer. Chem. Soc, 91, 5802 (1969);
25. H. Kuivila, Accounts Chem. Res., 1, 299 (1968).
26. Studies of spin trapping and chemically induced dynamic polarization are in progress [cf. E. G. Janzen, Accounts Chem. Res., 4, 31 (1971),
27. and H. R. Ward, R. G. Lawler, and T. A. Marzilli, Tetrahedron Lett., 521 (1970)].
28. G. M. Whitesides and C. P. Casey, J. Amer. Chem. Soc, 88, 4541 (1966).
29. This assumes that alkane and alkene are formed by processes first order in organosilver(I) [cf. G. M. Whitesides, et al., J. Amer. Chem. Soc, 92, 1426 (1970)].