Organoactinide-catalyzed intermolecular hydroamination of terminal alkynes

Organometallics

Volumn 15, Issue 18, 1996, Pages 3773-3775

  Haskel, Ariel ^a   Straub, Thomas ^a   Eisen, Moris S ^a  

^a TECHNION ISRAEL INSTITUTE OF TECHNOLOGY   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001239239     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om960182z     Document Type: Article

References (33)

1. (a) For a review of additions of amines to alkenes, see: Gasc, M. B.; Latties, A.; Perie, J. J. Tetrahedron 1983, 339, 703. (b) For a review of addition of amines to alkynes, see: Jäger, V.; Viehe, H. G. HoubenWeyl, Methoden der Organischen Chemie; Thieme Verlag: Stuttgart, Germany, 1977; Vol. 5/2a, p 713.
2. (a) For a review of additions of amines to alkenes, see: Gasc, M. B.; Latties, A.; Perie, J. J. Tetrahedron 1983, 339, 703. (b) For a review of addition of amines to alkynes, see: Jäger, V.; Viehe, H. G. HoubenWeyl, Methoden der Organischen Chemie; Thieme Verlag: Stuttgart, Germany, 1977; Vol. 5/2a, p 713.
3. (a) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry; University Science Books: Mill Valley, CA, 1987; Chapters 7.4, 17.1 and references therein.
4. (b) Nugent, W. A.; Mayer, J. A. Metal-Ligand Multiple Bonds; Wiley-Interscience: New York, 1988.
5. (a) Giardello, M. A.; Conticello, V. P.; Brard, L.; Gagné, M. R.; Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10241-10234.
6. (b) Gagné, M. R.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1992, 114, 275-294.
7. (c) Hegedus, L. S. Angew. Chem., Int. Ed. Engl. 1988, 27, 1113-1314.
8. (a) Li, Y.; Fu, P.-F.; Marks, T. J. Organometallics 1994, 13, 439-440.
9. (b) McGrane, P. L.; Livinghouse, T. J. Am. Chem. Soc. 1993, 115, 11485-11489.
10. (c) McGrane, P. L.; Jensen, M.; Livinghouse, T. J. Am. Chem Soc. 1992, 114, 5459-5460.
11. Casalnuovo, A. L.; Calabbreses, J. C.; Milstein, D. J. Am. Chem. Soc. 1988, 110, 6738-6740.
12. (a) Walsh, P. J.; Baranger, A. M.; Bergman, R. G. J. Am. Chem. Soc. 1992, 114, 1708-1719.
13. (b) Baranger, A. M.; Walsh, P. J.; Bergman, R. G. J. Am. Chem. Soc. 1993, 115, 2753-2763 and references therein.
14. Li, Y.; Marks, T. J. Organometallics 1996, 75, 3770.
15. Straub, T.; Haskel, A.; Eisen, M. S. J. Am. Chem. Soc. 1995, 117, 6364-6365.
16. 13C, GC/MS, and high-resolution MS spectroscopy; see Supporting Information, (a) Fry, J. L. J. Chem. Soc., Chem. Commun. 1974, 45. (b) Karabatsos, G. L.; Lande, S. S. Tetrahedron 1968, 24, 3907-3922.
17. 13C, GC/MS, and high-resolution MS spectroscopy; see Supporting Information, (a) Fry, J. L. J. Chem. Soc., Chem. Commun. 1974, 45. (b) Karabatsos, G. L.; Lande, S. S. Tetrahedron 1968, 24, 3907-3922.
18. Haskel, A.; Straub, T.; Eisen, M. S. Manuscript in preparation.
19. (a) Hitchcock, P. B.; Lappert, M. F.; Liu, D. S. J. Chem. Soc., Chem. Commun. 1994, 1699.
20. (b) Eisen, M. S.; Kapon, M. J. Chem. Soc., Dalton Trans. 1994, 3507.
21. Thermodynamically, the enthalpy for this step can be calculated to be exothermic for both actinides (ΔH(Th) ≈ -17 kcal/mol and ΔU(U) ≈ -9 kcal/mol). (a) Giardello, M. A.; King, W. A.; Nolan, S. P.; Porchia, M.; Sishta, C.; Marks, T. J. In Energetics of Organometallic Species; Simões, M. J. A., Ed.; Kluwer Academic Press: Dordrecht, The Netherlands, 1992; pp 35-51 and references therein. (b) Simões, M. J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688.
22. Thermodynamically, the enthalpy for this step can be calculated to be exothermic for both actinides (ΔH(Th) ≈ -17 kcal/mol and ΔU(U) ≈ -9 kcal/mol). (a) Giardello, M. A.; King, W. A.; Nolan, S. P.; Porchia, M.; Sishta, C.; Marks, T. J. In Energetics of Organometallic Species; Simões, M. J. A., Ed.; Kluwer Academic Press: Dordrecht, The Netherlands, 1992; pp 35-51 and references therein. (b) Simões, M. J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688.
23. For lanthanides, analog complexes have been characterized, see refs 3a,b. Attempts of trapping complex I at low temperatures have been unsuccessful.
24. (a) Characterization, solid-state structure, and reactivity toward alkynes of a bis(amido) complex A (Ac = U; R = 2,6-dimethylphenyl): Straub, T.; Frank, W.; Reiss, G. J.; Eisen, M. S. J. Chem. Soc., Dalton Trans., in press. (b) Fagan, P. J.; Manriquez, J. M.; Vollmer, S. H.; Day, C. S.; Day, V. W.; Marks, T. J. J. Am. Chem. Soc. 1981, 103, 2206-2220.
25. (a) Characterization, solid-state structure, and reactivity toward alkynes of a bis(amido) complex A (Ac = U; R = 2,6-dimethylphenyl): Straub, T.; Frank, W.; Reiss, G. J.; Eisen, M. S. J. Chem. Soc., Dalton Trans., in press. (b) Fagan, P. J.; Manriquez, J. M.; Vollmer, S. H.; Day, C. S.; Day, V. W.; Marks, T. J. J. Am. Chem. Soc. 1981, 103, 2206-2220.
26. Pathway to complex H (step 8) was observed for Th complexes inducing the production of selective oligomers. For uranium complexes, this equilibrium pathway involving the bis(amido)/bis(acetylide) complex is not observed.
27. w = 0.033, and GOF = 1.53.
28. For a base-free uranium-imido complex see: Arney, D. S. J.; Burns, C. J. J. Am. Chem. Soc. 1995, 117, 9448-9460.
29. The Th-alkenyl bond is stronger than the Th-N bond by ≈10 kcal/mol; see ref 10.
30. 2 by the anti-addition of the alkyne is more stable than the corresponding enamine by the following: TMSC=CH, ≈2.1 kcal/mol; n-BuC≡CH, ≈3.5 kcal/mol; PhC≡CH, ≈1.4 kcal/mol.
31. (a) Fendrick, C. M.; Schertz, L. D.; Day, V. W.; Marks, T. J. J. Am. Chem. Soc. 1988, 7, 1828-1838.
32. (b) Lin, Z.; Marks, T. J. J. Am. Chem. Soc. 1990, 112, 5515-5525.
33. 2 complexes. [Catalyst] = 0.015-0.078 M; [amine] = 0.70-4.26 M; [alkyne] = 0.75-4.20 M.