The Use of 15N NMR Spectroscopy to Resolve the "Higher Order Cyanocuprate" Controversy: 15N, 6Li, and 13C NMR Spectroscopic Investigations of CuCN-Derived Butyl Cuprates

Angewandte Chemie - International Edition

Volumn 37, Issue 3, 1998, Pages 314-317

  Bertz, Steven H ^a   Nilsson, Karolina ^c   Davidsson, Öjvind ^c   Snyder, James P ^b  

^a Complexity Study Center ^*  (United States)

^b EMORY UNIVERSITY   (United States)

^c NONE

Author keywords

Aggregations; Copper; Density functional calculations; Lithium; Nmr spectroscopy

Indexed keywords

EID: 0032536467     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19980216)37:3<314::AID-ANIE314>3.0.CO;2-T     Document Type: Article

References (47)

1. For earlier uses of CuCN in organocopper chemistry, see a) N. V. Kondyreva, D. A. Fomina, Zh. Russ. Fiz.-Khim. O-va, Chast Khim. 1915, 47, 190-198; b) H. Gilman, J. M. Straley, Rec. Trav. Chim. Pays-Bas. 1936, 55, 821-834.
2. For earlier uses of CuCN in organocopper chemistry, see a) N. V. Kondyreva, D. A. Fomina, Zh. Russ. Fiz.-Khim. O-va, Chast Khim. 1915, 47, 190-198; b) H. Gilman, J. M. Straley, Rec. Trav. Chim. Pays-Bas. 1936, 55, 821-834.
3. J.-P. Gorlier, L. Hamon, J. Levisalles, J. Wagnon, J. Chem., Soc. Chem. Commun. 1973, 88.
4. S. H. Bertz, J. Am. Chem. Soc. 1991, 113, 5470-5471.
5. B. H. Lipshutz, R. S. Wilhelm, D. M. Floyd, J. Am. Chem. Soc. 1981, 103, 7672-7674.
6. a) B. H. Lipshutz, J. A. Kozlowski, R. S. Wilhelm, J. Org. Chem. 1984, 49, 3943-3949;
7. b) See also B. H. Lipshutz, S. Sharma, E. L. Ellsworth, J. Am. Chem. Soc. 1990, 112, 4032-4034.
8. S. H. Bertz, J. Am. Chem. Soc. 1990, 112, 4031-4032.
9. 1 dianionic salts."
10. b) See also B. H. Lipshutz, B. James, J. Org. Chem. 1994, 59, 7585-7587.
11. a) T. Stemmler, J. E. Penner-Hahn, P. Knochel, J. Am. Chem. Soc. 1993, 115, 348-350;
12. b) T. M. Barnhart, H. Huang, J. E. Penner-Hahn, J. Org. Chem. 1995, 60, 4310-4311;
13. c) T. M. Barnhart, J. E. Penner-Hahn, Physica B 1995, 208&209, 709-710.
14. T. L. Stemmler, T. M. Barnhart, J. E. Penner-Hahn, C. E. Tucker, P. Knochel, M. Böhme, G. Frenking, J. Am. Chem. Soc. 1995, 117, 12489-12497.
15. H. Huang, K. Alvarez, Q. Lui, T. M. Barnhart, J. P. Snyder, J. E. Penner-Hahn, J. Am. Chem. Soc. 1996, 118, 8808-8816.
16. a) J. P. Snyder, S. H. Bertz, J. Org. Chem, 1995, 60, 4312-4313;
17. b) J. P. Snyder, D. P. Spangler, J. R. Behling, B. E. Rossiter, ibid. 1994, 59, 2665-2667;
18. c) J. P. Snyder, G. E. Tipsword, D. P. Spangler, J. Am. Chem. Soc. 1992, 114, 1507-1510.
19. 6Li was prepared in pentane by the method of G. Hilmersson, Ö. Davidsson, Organometallics 1995, 14, 912-918;
20. b) NMR samples were prepared as described in S. H. Bertz, A. S. Vellekoop, R. A. J. Smith, J. P. Snyder, ibid. 1995, 14, 1213-1220, except that 5 mm tubes were used instead of 10mm. See also Experimental Section.
21. a) B. Wrackmeyer, Z. Naturforsch. B 1988, 43, 923-926;
22. b) D. E. J. Arnold, S. Cradock, E. A. V. Ebsworth, J. D. Murdoch, D. W. H. Rankin, D. C. J. Skea, R. K. Harris, B. J. Kimber J. Chem. Soc. Dalton Trans. 1981, 1349-1351;
23. 8]THF, we measure δ = -81.7 on this scale. Since the calculated shifts are referenced to the same value as the experimental ones, our conclusions are independent of the standard.
24. a) G. Fraenkel, A. M. Fraenkel, M. J. Geckle, F. Schloss, J. Am. Chem. Soc. 1979, 101, 4745-4747;
25. b) D. Seebach, R. Hässig, J. Gabriel, Helv. Chim. Acta 1983, 66, 308-337;
26. c) for a recent review see Lithium Chemistry-A Theoretical and Experimental Overview (Eds.: A.-M. Saspe, P. von R. Schleyer), Wiley, Chichester, 1995.
27. 2CuLi: S. H. Bertz, G. Dabbagh, X. He, P. P. Power, J. Am. Chem. Soc, 1993, 115, 11640-11641.
28. 6Li spectrum of the 2:1 reagent which may be attributable to CN-free cuprates, presumably similar to "halide-free" cuprates: E. C. Ashby, J. J. Watkins, J. Am. Chem. Soc. 1977, 99, 5312-5317;
29. b) see also reference [25a].
30. 6Li by a standard addition experiment.
31. 10]diethyl ether/pentane.
32. a) D. B. Chesnut, Rev. Comput. Chem. 1996, 8, 245-297;
33. b) D. B. Chesnut, Ann. Rep. NMR Spectr. 1994,29, 71-122:
34. c) D. B. Chesnut, B. E. Rusiloski, K. D. Moore, D. A. Egolf, J. Comput. Chem. 1993, 14, 1364-1375;
35. d) D. B. Chesnut, K. D. Moore, ibid. 1989, 10, 648-659.
36. a) A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652;
37. b) P. J. Stevens, F. F. Devlin, C. F. Chablowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11623-11627.
38. 15N NMR shifts as in reference [13], for example, TMSCN at δ = 77.7.
39. a) T. A. Mobley, F. Müller, S. Berger, J. Am. Chem. Soc. 1998, 120, in press;
40. b) A. Gerold, J. T. B. M. Jastrzebski, C. M. P. Kronenburg, N. Krause, G. van Koten, Angew. Chem. 1997, 109, 778-780; Angew. Chem. Int. Ed. Engl. 1997, 36, 755-757.
41. b) A. Gerold, J. T. B. M. Jastrzebski, C. M. P. Kronenburg, N. Krause, G. van Koten, Angew. Chem. 1997, 109, 778-780; Angew. Chem. Int. Ed. Engl. 1997, 36, 755-757.
42. a) S. H. Bertz, E. H. Fairchild in Encyclopedia of Reagents for Organic Synthesis. (Ed.: L. Paquette), Wiley, New York, 1995, pp, 1312-1315 (CuBr), 1341-1343 (CuCN), 1346-1349 (CuI);
43. b) S. H. Bertz, G. Dabbagh, L. M. Williams, J. Org. Chem. 1985, 50, 4414-4415 (CuOTf).
44. 2: Discrete Reagents or 'Lower Order' LiCN-Modified Oilman Cuprates?"
45. Two classes of bona fide higher order cuprates that do not contain CN are known: a) S. H. Bertz, G. Dabbagh. J. Am. Chem. Soc. 1988, 110, 3668-3670 (aryl); b) F. Olbrich, J. Kopf, E. Weiss, Angew. Chem. 1993, 105, 1136-1138; Angew. Chem. Int. Ed. Engl. 1993, 32, 1077-1079 (alkynyl).
46. Two classes of bona fide higher order cuprates that do not contain CN are known: a) S. H. Bertz, G. Dabbagh. J. Am. Chem. Soc. 1988, 110, 3668-3670 (aryl); b) F. Olbrich, J. Kopf, E. Weiss, Angew. Chem. 1993, 105, 1136-1138; Angew. Chem. Int. Ed. Engl. 1993, 32, 1077-1079 (alkynyl).
47. Two classes of bona fide higher order cuprates that do not contain CN are known: a) S. H. Bertz, G. Dabbagh. J. Am. Chem. Soc. 1988, 110, 3668-3670 (aryl); b) F. Olbrich, J. Kopf, E. Weiss, Angew. Chem. 1993, 105, 1136-1138; Angew. Chem. Int. Ed. Engl. 1993, 32, 1077-1079 (alkynyl).