Nucleophilic aromatic substitution reactions of borabenzene-trimethylphosphine: A versatile route to 1-substituted boratabenzenes

Journal of the American Chemical Society

Volumn 118, Issue 26, 1996, Pages 6329-6330

  Qiao, Shuang ^a   Hoic, Diego A ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ORGANOBORON DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0030018445     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960938l     Document Type: Article

References (41)

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2. (b) Boese, R.; Finke, N.; Keil, T.; Paetzold, P.; Schmid, G. Z. Naturforsch., B 1985, 40, 1327-1332.
3. (c) Hoic, D. A.; Wolf, J. R.; Davis, W. M.; Fu, G. C. Organometallics 1996, 15, 1315-1318.
4. For leading references, see: March, J. Advanced Organic Chemistry; Wiley: New York, 1992; Chapter 13.
5. For leading references, see: Boulton, A. J.; McKillop, A. In Comprehensive Heterocyclic Chemistry; Boulton, A. J., McKillop, A., Eds.; Pergamon: New York, 1984; Vol. 2, Chapter 2.02.
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7. Herberich (Herberich, G. E.; Greiss, G.; Heil, H. F.; Muller, J. J. Chem. Soc., Chem. Commun. 1971, 1328-1329) and Ashe (Ashe, A. J., III; Butler, W.; Sandford, H. F. J. Am. Chem. Soc. 1979, 101, 7066-7067) have established that boratabenzenes (2) which are π-bound to transition metals can undergo nucleophilic aromatic substitution.
8. Herberich (Herberich, G. E.; Greiss, G.; Heil, H. F.; Muller, J. J. Chem. Soc., Chem. Commun. 1971, 1328-1329) and Ashe (Ashe, A. J., III; Butler, W.; Sandford, H. F. J. Am. Chem. Soc. 1979, 101, 7066-7067) have established that boratabenzenes (2) which are π-bound to transition metals can undergo nucleophilic aromatic substitution.
9. For a review of boratabenzene chemistry, see: Herberich, G. E.; Ohst, H. Adv. Organomel. Chem. 1986, 25, 199-236.
10. For applications of boratabenzene-metal complexes in catalysis, see: (a) Bazan, G. C.; Rodriguez, G.; Ashe, A. J., III; Al-Ahmad, S.; Muller, C. J. Am. Chem. Soc. 1996, 118, 2291-2292. (b) Bonnemann, H.; Brijoux, W.; Brinkmann, R.; Meurers, W. Helv. Chim. Acta 1984, 67, 1616-1624.
11. For applications of boratabenzene-metal complexes in catalysis, see: (a) Bazan, G. C.; Rodriguez, G.; Ashe, A. J., III; Al-Ahmad, S.; Muller, C. J. Am. Chem. Soc. 1996, 118, 2291-2292. (b) Bonnemann, H.; Brijoux, W.; Brinkmann, R.; Meurers, W. Helv. Chim. Acta 1984, 67, 1616-1624.
12. 5BNMeBn): Ashe, A. J., III; Kampf, J. W.; Muller, C.; Schneider, M. Organometallics 1996, 15, 387-393.
13. 5BNMeBn): Ashe, A. J., III; Kampf, J. W.; Muller, C.; Schneider, M. Organometallics 1996, 15, 387-393.
14. 5BNMeBn): Ashe, A. J., III; Kampf, J. W.; Muller, C.; Schneider, M. Organometallics 1996, 15, 387-393.
15. 5BNMeBn): Ashe, A. J., III; Kampf, J. W.; Muller, C.; Schneider, M. Organometallics 1996, 15, 387-393.
16. 5BNMeBn): Ashe, A. J., III; Kampf, J. W.; Muller, C.; Schneider, M. Organometallics 1996, 15, 387-393.
17. Synthesized in three steps from commercially available 1-trimethylsilyl-1,4-pentadiyne (ref 1c). Preliminary experiments indicate that other borabenzene - ligand complexes can also be used in certain instances.
18. (a) We agree with a referee that, a priori, the borabenzyne mechanism is the least likely of these three possibilities. (b) We have also considered a radical process involving electron transfer (for a review, see: Norris. R. K. In Comprehensive Organic Chemistry; Trost, B. M., Ed.; Pergamon: New York, 1991; Vol. 4, Chapter 2.2.). The highly reproducible kinetics that we observe for the reaction of borabenzene-PMe3 with lithium trimethylsilylacetylide, essentially independent of the presence or absence of light or oxygen, suggests, however, that a radical pathway is not operative.
19. (a) We agree with a referee that, a priori, the borabenzyne mechanism is the least likely of these three possibilities. (b) We have also considered a radical process involving electron transfer (for a review, see: Norris. R. K. In Comprehensive Organic Chemistry; Trost, B. M., Ed.; Pergamon: New York, 1991; Vol. 4, Chapter 2.2.). The highly reproducible kinetics that we observe for the reaction of borabenzene-PMe3 with lithium trimethylsilylacetylide, essentially independent of the presence or absence of light or oxygen, suggests, however, that a radical pathway is not operative.
20. 3 with lithium trimethylsilylacetylide that we have monitored by NMR spectroscopy.
21. 3 in order to obtain reproducible kinetic data.
22. (a) Maier, G. Pure Appl. Chem. 1986, 58, 95-104.
23. (b) Maier, G.; Reisenauer, H. P.; Henkelmann, J.; Kliche, C. Angew. Chem., Int. Ed. Engl. 1988, 27, 295-296. See also: Maier, G.; Wolf, H.-J.; Boese, R. Chem. Ber. 1990, 123, 505-511.
24. (b) Maier, G.; Reisenauer, H. P.; Henkelmann, J.; Kliche, C. Angew. Chem., Int. Ed. Engl. 1988, 27, 295-296. See also: Maier, G.; Wolf, H.-J.; Boese, R. Chem. Ber. 1990, 123, 505-511.
25. For computational studies of borabenzene, see: (a) Schulman, J. M.; Disch, R. L.; Sabio, M. I. J. Am. Chem. Soc. 1982, 104, 3785-3788. (b) Raabe, G.; Heyne, E.; Schleker, W.; Fleischhauer, J. Z. Naturforsch., A 1984, 39, 678-681. (c) Raabe, G.; Schleker, W.; Heyne, E.; Fleischhauer, J. Z. Naturforsch., A 1987,42, 352-360. (d) Schulman, J. M.; Disch, R. L. Organometallics 1989, 8, 733-737. (e) Cioslowski, J.; Hay, P. J. J. Am. Chem. Soc. 1990, 112, 1707-1710.
26. For computational studies of borabenzene, see: (a) Schulman, J. M.; Disch, R. L.; Sabio, M. I. J. Am. Chem. Soc. 1982, 104, 3785-3788. (b) Raabe, G.; Heyne, E.; Schleker, W.; Fleischhauer, J. Z. Naturforsch., A 1984, 39, 678-681. (c) Raabe, G.; Schleker, W.; Heyne, E.; Fleischhauer, J. Z. Naturforsch., A 1987,42, 352-360. (d) Schulman, J. M.; Disch, R. L. Organometallics 1989, 8, 733-737. (e) Cioslowski, J.; Hay, P. J. J. Am. Chem. Soc. 1990, 112, 1707-1710.
27. For computational studies of borabenzene, see: (a) Schulman, J. M.; Disch, R. L.; Sabio, M. I. J. Am. Chem. Soc. 1982, 104, 3785-3788. (b) Raabe, G.; Heyne, E.; Schleker, W.; Fleischhauer, J. Z. Naturforsch., A 1984, 39, 678-681. (c) Raabe, G.; Schleker, W.; Heyne, E.; Fleischhauer, J. Z. Naturforsch., A 1987,42, 352-360. (d) Schulman, J. M.; Disch, R. L. Organometallics 1989, 8, 733-737. (e) Cioslowski, J.; Hay, P. J. J. Am. Chem. Soc. 1990, 112, 1707-1710.
28. For computational studies of borabenzene, see: (a) Schulman, J. M.; Disch, R. L.; Sabio, M. I. J. Am. Chem. Soc. 1982, 104, 3785-3788. (b) Raabe, G.; Heyne, E.; Schleker, W.; Fleischhauer, J. Z. Naturforsch., A 1984, 39, 678-681. (c) Raabe, G.; Schleker, W.; Heyne, E.; Fleischhauer, J. Z. Naturforsch., A 1987,42, 352-360. (d) Schulman, J. M.; Disch, R. L. Organometallics 1989, 8, 733-737. (e) Cioslowski, J.; Hay, P. J. J. Am. Chem. Soc. 1990, 112, 1707-1710.
29. For computational studies of borabenzene, see: (a) Schulman, J. M.; Disch, R. L.; Sabio, M. I. J. Am. Chem. Soc. 1982, 104, 3785-3788. (b) Raabe, G.; Heyne, E.; Schleker, W.; Fleischhauer, J. Z. Naturforsch., A 1984, 39, 678-681. (c) Raabe, G.; Schleker, W.; Heyne, E.; Fleischhauer, J. Z. Naturforsch., A 1987,42, 352-360. (d) Schulman, J. M.; Disch, R. L. Organometallics 1989, 8, 733-737. (e) Cioslowski, J.; Hay, P. J. J. Am. Chem. Soc. 1990, 112, 1707-1710.
30. For leading references to studies of the isoelectronic phenyl cation, see: (a) Stang, P. J.; Rappoport, Z.; Hanack, M.; Subramanian, L. R. Vinyl Cations; Academic: New York, 1979. (b) Ambroz, H. B.; Kemp, T. J. Chem. Soc. Rev. 1979, 8, 353-365. (c) Apeloig, Y.; Arad, D. J. Am. Chem. Soc. 1985, 107, 5285-5286. (d) Himeshima, Y.; Kobayashi, H.; Sonoda, T. J Am. Chem. Soc. 1985, 107, 5286-5288. (e) Gasper, S. M.; Davadoss, C.; Schuster, G. B. J. Am. Chem. Soc. 1995, 117, 5206-5211.
31. For leading references to studies of the isoelectronic phenyl cation, see: (a) Stang, P. J.; Rappoport, Z.; Hanack, M.; Subramanian, L. R. Vinyl Cations; Academic: New York, 1979. (b) Ambroz, H. B.; Kemp, T. J. Chem. Soc. Rev. 1979, 8, 353-365. (c) Apeloig, Y.; Arad, D. J. Am. Chem. Soc. 1985, 107, 5285-5286. (d) Himeshima, Y.; Kobayashi, H.; Sonoda, T. J Am. Chem. Soc. 1985, 107, 5286-5288. (e) Gasper, S. M.; Davadoss, C.; Schuster, G. B. J. Am. Chem. Soc. 1995, 117, 5206-5211.
32. For leading references to studies of the isoelectronic phenyl cation, see: (a) Stang, P. J.; Rappoport, Z.; Hanack, M.; Subramanian, L. R. Vinyl Cations; Academic: New York, 1979. (b) Ambroz, H. B.; Kemp, T. J. Chem. Soc. Rev. 1979, 8, 353-365. (c) Apeloig, Y.; Arad, D. J. Am. Chem. Soc. 1985, 107, 5285-5286. (d) Himeshima, Y.; Kobayashi, H.; Sonoda, T. J Am. Chem. Soc. 1985, 107, 5286-5288. (e) Gasper, S. M.; Davadoss, C.; Schuster, G. B. J. Am. Chem. Soc. 1995, 117, 5206-5211.
33. For leading references to studies of the isoelectronic phenyl cation, see: (a) Stang, P. J.; Rappoport, Z.; Hanack, M.; Subramanian, L. R. Vinyl Cations; Academic: New York, 1979. (b) Ambroz, H. B.; Kemp, T. J. Chem. Soc. Rev. 1979, 8, 353-365. (c) Apeloig, Y.; Arad, D. J. Am. Chem. Soc. 1985, 107, 5285-5286. (d) Himeshima, Y.; Kobayashi, H.; Sonoda, T. J Am. Chem. Soc. 1985, 107, 5286-5288. (e) Gasper, S. M.; Davadoss, C.; Schuster, G. B. J. Am. Chem. Soc. 1995, 117, 5206-5211.
34. For leading references to studies of the isoelectronic phenyl cation, see: (a) Stang, P. J.; Rappoport, Z.; Hanack, M.; Subramanian, L. R. Vinyl Cations; Academic: New York, 1979. (b) Ambroz, H. B.; Kemp, T. J. Chem. Soc. Rev. 1979, 8, 353-365. (c) Apeloig, Y.; Arad, D. J. Am. Chem. Soc. 1985, 107, 5285-5286. (d) Himeshima, Y.; Kobayashi, H.; Sonoda, T. J Am. Chem. Soc. 1985, 107, 5286-5288. (e) Gasper, S. M.; Davadoss, C.; Schuster, G. B. J. Am. Chem. Soc. 1995, 117, 5206-5211.
35. For a discussion of benzyne chemistry, see ref 2.
36. 9) is treated with lithium trimethylsilylacetylide, all of the deuterium remains in the phosphine methyl groups.
37. For leading references, see: Semmelhack, M. F. In Comprehensive Organometaliic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995.
38. For structural studies of lithium tert-butylacetylide, see: (a) Fraenkel, G. Polym. Prepr., Am. Chem. Soc. Div. Polym. Chem. 1986, 27, 132-133. (b) Fraenkel, G.; Pramanik, P. J. Chem. Soc., Chem. Commun. 1983, 1527-1529. (c) Bauer, W.; Seebach, D. Helv. Chim. Acta 1984, 67, 1972-1988. (d) Geissler, M.; Kopf, J.; Schubert, B.; Weiss, E.; Neugebauer, W.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1987, 26, 587-588.
39. For structural studies of lithium tert-butylacetylide, see: (a) Fraenkel, G. Polym. Prepr., Am. Chem. Soc. Div. Polym. Chem. 1986, 27, 132-133. (b) Fraenkel, G.; Pramanik, P. J. Chem. Soc., Chem. Commun. 1983, 1527-1529. (c) Bauer, W.; Seebach, D. Helv. Chim. Acta 1984, 67, 1972-1988. (d) Geissler, M.; Kopf, J.; Schubert, B.; Weiss, E.; Neugebauer, W.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1987, 26, 587-588.
40. For structural studies of lithium tert-butylacetylide, see: (a) Fraenkel, G. Polym. Prepr., Am. Chem. Soc. Div. Polym. Chem. 1986, 27, 132-133. (b) Fraenkel, G.; Pramanik, P. J. Chem. Soc., Chem. Commun. 1983, 1527-1529. (c) Bauer, W.; Seebach, D. Helv. Chim. Acta 1984, 67, 1972-1988. (d) Geissler, M.; Kopf, J.; Schubert, B.; Weiss, E.; Neugebauer, W.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1987, 26, 587-588.
41. For structural studies of lithium tert-butylacetylide, see: (a) Fraenkel, G. Polym. Prepr., Am. Chem. Soc. Div. Polym. Chem. 1986, 27, 132-133. (b) Fraenkel, G.; Pramanik, P. J. Chem. Soc., Chem. Commun. 1983, 1527-1529. (c) Bauer, W.; Seebach, D. Helv. Chim. Acta 1984, 67, 1972-1988. (d) Geissler, M.; Kopf, J.; Schubert, B.; Weiss, E.; Neugebauer, W.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1987, 26, 587-588.