Organolanthanide-catalyzed imine hydrogenation. Scope, selectivity, mechanistic observations, and unusual byproducts

Journal of the American Chemical Society

Volumn 119, Issue 16, 1997, Pages 3745-3755

  Obora, Yasushi ^a   Ohta, Tetsuo ^a   Stern, Charlotte L ^a   Marks, Tobin J ^a  

^a NORTHWESTERN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE;

ARTICLE; CATALYSIS; CRYSTALLOGRAPHY; DRUG SYNTHESIS; IN VITRO STUDY; METHODOLOGY; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030971070     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja963775+     Document Type: Article

References (102)

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4. Heats of hydrogenation were computed using the AM1 Hamiltonian in the MOPAC molecular orbital package.
5. For some recent examples of the homogeneous hydrogenation of imines and related substrates, see: (a) Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Hegedus, L. S., Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Elsevier: Oxford, 1995; Vol. 12, pp 26-27 and references therein. (b) Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley: New York, 1994; pp 82-85 and references therein. (c) Ball, G. E.; Cullen, W. R.; Fryzuk, M. D.; Henderson, W. J.; James, B. R.; MacFarlane, K. S. Inorg. Chem. 1994, 33, 1464-1468. (d) Bolm, C. Angew. Chem., Int. Ed. Engl. 1993, 32, 232-234. (e) Takaya, H.; Ohta, T.; Noyori, R. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers: New York, 1993; Chapter 1 and references therein. (f) Burk, M. J.; Feaster, J. E. J. Am. Chem. Soc. 1992, 114, 626-627. (g) Becalski, A. G.; Cullen, W. R.; Fryzuk, M. D.; James, B. R.; Kang, G.-J.; Rettig, S. J. Inorg. Chem. 1991, 30, 5002-5008. (h) Spindler, F.; Pugin, B.; Blaser, H.-U. Angew. Chem., Int. Ed. Engl. 1990, 29, 558-559.
6. For some recent examples of the homogeneous hydrogenation of imines and related substrates, see: (a) Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Hegedus, L. S., Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Elsevier: Oxford, 1995; Vol. 12, pp 26-27 and references therein. (b) Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley: New York, 1994; pp 82-85 and references therein. (c) Ball, G. E.; Cullen, W. R.; Fryzuk, M. D.; Henderson, W. J.; James, B. R.; MacFarlane, K. S. Inorg. Chem. 1994, 33, 1464-1468. (d) Bolm, C. Angew. Chem., Int. Ed. Engl. 1993, 32, 232-234. (e) Takaya, H.; Ohta, T.; Noyori, R. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers: New York, 1993; Chapter 1 and references therein. (f) Burk, M. J.; Feaster, J. E. J. Am. Chem. Soc. 1992, 114, 626-627. (g) Becalski, A. G.; Cullen, W. R.; Fryzuk, M. D.; James, B. R.; Kang, G.-J.; Rettig, S. J. Inorg. Chem. 1991, 30, 5002-5008. (h) Spindler, F.; Pugin, B.; Blaser, H.-U. Angew. Chem., Int. Ed. Engl. 1990, 29, 558-559.
7. For some recent examples of the homogeneous hydrogenation of imines and related substrates, see: (a) Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Hegedus, L. S., Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Elsevier: Oxford, 1995; Vol. 12, pp 26-27 and references therein. (b) Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley: New York, 1994; pp 82-85 and references therein. (c) Ball, G. E.; Cullen, W. R.; Fryzuk, M. D.; Henderson, W. J.; James, B. R.; MacFarlane, K. S. Inorg. Chem. 1994, 33, 1464-1468. (d) Bolm, C. Angew. Chem., Int. Ed. Engl. 1993, 32, 232-234. (e) Takaya, H.; Ohta, T.; Noyori, R. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers: New York, 1993; Chapter 1 and references therein. (f) Burk, M. J.; Feaster, J. E. J. Am. Chem. Soc. 1992, 114, 626-627. (g) Becalski, A. G.; Cullen, W. R.; Fryzuk, M. D.; James, B. R.; Kang, G.-J.; Rettig, S. J. Inorg. Chem. 1991, 30, 5002-5008. (h) Spindler, F.; Pugin, B.; Blaser, H.-U. Angew. Chem., Int. Ed. Engl. 1990, 29, 558-559.
8. For some recent examples of the homogeneous hydrogenation of imines and related substrates, see: (a) Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Hegedus, L. S., Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Elsevier: Oxford, 1995; Vol. 12, pp 26-27 and references therein. (b) Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley: New York, 1994; pp 82-85 and references therein. (c) Ball, G. E.; Cullen, W. R.; Fryzuk, M. D.; Henderson, W. J.; James, B. R.; MacFarlane, K. S. Inorg. Chem. 1994, 33, 1464-1468. (d) Bolm, C. Angew. Chem., Int. Ed. Engl. 1993, 32, 232-234. (e) Takaya, H.; Ohta, T.; Noyori, R. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers: New York, 1993; Chapter 1 and references therein. (f) Burk, M. J.; Feaster, J. E. J. Am. Chem. Soc. 1992, 114, 626-627. (g) Becalski, A. G.; Cullen, W. R.; Fryzuk, M. D.; James, B. R.; Kang, G.-J.; Rettig, S. J. Inorg. Chem. 1991, 30, 5002-5008. (h) Spindler, F.; Pugin, B.; Blaser, H.-U. Angew. Chem., Int. Ed. Engl. 1990, 29, 558-559.
9. For some recent examples of the homogeneous hydrogenation of imines and related substrates, see: (a) Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Hegedus, L. S., Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Elsevier: Oxford, 1995; Vol. 12, pp 26-27 and references therein. (b) Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley: New York, 1994; pp 82-85 and references therein. (c) Ball, G. E.; Cullen, W. R.; Fryzuk, M. D.; Henderson, W. J.; James, B. R.; MacFarlane, K. S. Inorg. Chem. 1994, 33, 1464-1468. (d) Bolm, C. Angew. Chem., Int. Ed. Engl. 1993, 32, 232-234. (e) Takaya, H.; Ohta, T.; Noyori, R. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers: New York, 1993; Chapter 1 and references therein. (f) Burk, M. J.; Feaster, J. E. J. Am. Chem. Soc. 1992, 114, 626-627. (g) Becalski, A. G.; Cullen, W. R.; Fryzuk, M. D.; James, B. R.; Kang, G.-J.; Rettig, S. J. Inorg. Chem. 1991, 30, 5002-5008. (h) Spindler, F.; Pugin, B.; Blaser, H.-U. Angew. Chem., Int. Ed. Engl. 1990, 29, 558-559.
10. For some recent examples of the homogeneous hydrogenation of imines and related substrates, see: (a) Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Hegedus, L. S., Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Elsevier: Oxford, 1995; Vol. 12, pp 26-27 and references therein. (b) Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley: New York, 1994; pp 82-85 and references therein. (c) Ball, G. E.; Cullen, W. R.; Fryzuk, M. D.; Henderson, W. J.; James, B. R.; MacFarlane, K. S. Inorg. Chem. 1994, 33, 1464-1468. (d) Bolm, C. Angew. Chem., Int. Ed. Engl. 1993, 32, 232-234. (e) Takaya, H.; Ohta, T.; Noyori, R. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers: New York, 1993; Chapter 1 and references therein. (f) Burk, M. J.; Feaster, J. E. J. Am. Chem. Soc. 1992, 114, 626-627. (g) Becalski, A. G.; Cullen, W. R.; Fryzuk, M. D.; James, B. R.; Kang, G.-J.; Rettig, S. J. Inorg. Chem. 1991, 30, 5002-5008. (h) Spindler, F.; Pugin, B.; Blaser, H.-U. Angew. Chem., Int. Ed. Engl. 1990, 29, 558-559.
11. For some recent examples of the homogeneous hydrogenation of imines and related substrates, see: (a) Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Hegedus, L. S., Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Elsevier: Oxford, 1995; Vol. 12, pp 26-27 and references therein. (b) Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley: New York, 1994; pp 82-85 and references therein. (c) Ball, G. E.; Cullen, W. R.; Fryzuk, M. D.; Henderson, W. J.; James, B. R.; MacFarlane, K. S. Inorg. Chem. 1994, 33, 1464-1468. (d) Bolm, C. Angew. Chem., Int. Ed. Engl. 1993, 32, 232-234. (e) Takaya, H.; Ohta, T.; Noyori, R. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers: New York, 1993; Chapter 1 and references therein. (f) Burk, M. J.; Feaster, J. E. J. Am. Chem. Soc. 1992, 114, 626-627. (g) Becalski, A. G.; Cullen, W. R.; Fryzuk, M. D.; James, B. R.; Kang, G.-J.; Rettig, S. J. Inorg. Chem. 1991, 30, 5002-5008. (h) Spindler, F.; Pugin, B.; Blaser, H.-U. Angew. Chem., Int. Ed. Engl. 1990, 29, 558-559.
12. For some recent examples of the homogeneous hydrogenation of imines and related substrates, see: (a) Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Hegedus, L. S., Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Elsevier: Oxford, 1995; Vol. 12, pp 26-27 and references therein. (b) Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley: New York, 1994; pp 82-85 and references therein. (c) Ball, G. E.; Cullen, W. R.; Fryzuk, M. D.; Henderson, W. J.; James, B. R.; MacFarlane, K. S. Inorg. Chem. 1994, 33, 1464-1468. (d) Bolm, C. Angew. Chem., Int. Ed. Engl. 1993, 32, 232-234. (e) Takaya, H.; Ohta, T.; Noyori, R. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers: New York, 1993; Chapter 1 and references therein. (f) Burk, M. J.; Feaster, J. E. J. Am. Chem. Soc. 1992, 114, 626-627. (g) Becalski, A. G.; Cullen, W. R.; Fryzuk, M. D.; James, B. R.; Kang, G.-J.; Rettig, S. J. Inorg. Chem. 1991, 30, 5002-5008. (h) Spindler, F.; Pugin, B.; Blaser, H.-U. Angew. Chem., Int. Ed. Engl. 1990, 29, 558-559.
13. calCd sums for Scheme 1, steps i and ii, are in reasonable agreement with the estimated ΔH for imine hydrogenation. Metal-ligand bond enthalpies are from the following: (a) Giardello, M. A.; King, W. A.; Nolan S. P.; Porchia, M.; Sishta, C.; Marks, T. J. In Energetics of Organometallic Species; Martinho Simoes, J. A., Ed.; Kluwer: Dordrecht, The Netherlands, 1992; pp 35-54. (b) Nolan, S. P.; Stern, D.; Hedden, D.; Marks, T. J. ACS Symp. Ser. 1990, 428, 159-174. (c) Nolan, S. P.; Stern, D.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 7844-7853. (d) Schock, L. E.; Marks, T. J. J. Am. Chem. Soc. 1988, 110, 7701-7715. (e) Bruno, J. W.; Marks, T. J.; Morss, L. R. J. Am. Chem. Soc. 1983, 105, 6824-6832.
14. calCd sums for Scheme 1, steps i and ii, are in reasonable agreement with the estimated ΔH for imine hydrogenation. Metal-ligand bond enthalpies are from the following: (a) Giardello, M. A.; King, W. A.; Nolan S. P.; Porchia, M.; Sishta, C.; Marks, T. J. In Energetics of Organometallic Species; Martinho Simoes, J. A., Ed.; Kluwer: Dordrecht, The Netherlands, 1992; pp 35-54. (b) Nolan, S. P.; Stern, D.; Hedden, D.; Marks, T. J. ACS Symp. Ser. 1990, 428, 159-174. (c) Nolan, S. P.; Stern, D.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 7844-7853. (d) Schock, L. E.; Marks, T. J. J. Am. Chem. Soc. 1988, 110, 7701-7715. (e) Bruno, J. W.; Marks, T. J.; Morss, L. R. J. Am. Chem. Soc. 1983, 105, 6824-6832.
15. calCd sums for Scheme 1, steps i and ii, are in reasonable agreement with the estimated ΔH for imine hydrogenation. Metal-ligand bond enthalpies are from the following: (a) Giardello, M. A.; King, W. A.; Nolan S. P.; Porchia, M.; Sishta, C.; Marks, T. J. In Energetics of Organometallic Species; Martinho Simoes, J. A., Ed.; Kluwer: Dordrecht, The Netherlands, 1992; pp 35-54. (b) Nolan, S. P.; Stern, D.; Hedden, D.; Marks, T. J. ACS Symp. Ser. 1990, 428, 159-174. (c) Nolan, S. P.; Stern, D.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 7844-7853. (d) Schock, L. E.; Marks, T. J. J. Am. Chem. Soc. 1988, 110, 7701-7715. (e) Bruno, J. W.; Marks, T. J.; Morss, L. R. J. Am. Chem. Soc. 1983, 105, 6824-6832.
16. calCd sums for Scheme 1, steps i and ii, are in reasonable agreement with the estimated ΔH for imine hydrogenation. Metal-ligand bond enthalpies are from the following: (a) Giardello, M. A.; King, W. A.; Nolan S. P.; Porchia, M.; Sishta, C.; Marks, T. J. In Energetics of Organometallic Species; Martinho Simoes, J. A., Ed.; Kluwer: Dordrecht, The Netherlands, 1992; pp 35-54. (b) Nolan, S. P.; Stern, D.; Hedden, D.; Marks, T. J. ACS Symp. Ser. 1990, 428, 159-174. (c) Nolan, S. P.; Stern, D.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 7844-7853. (d) Schock, L. E.; Marks, T. J. J. Am. Chem. Soc. 1988, 110, 7701-7715. (e) Bruno, J. W.; Marks, T. J.; Morss, L. R. J. Am. Chem. Soc. 1983, 105, 6824-6832.
17. calCd sums for Scheme 1, steps i and ii, are in reasonable agreement with the estimated ΔH for imine hydrogenation. Metal-ligand bond enthalpies are from the following: (a) Giardello, M. A.; King, W. A.; Nolan S. P.; Porchia, M.; Sishta, C.; Marks, T. J. In Energetics of Organometallic Species; Martinho Simoes, J. A., Ed.; Kluwer: Dordrecht, The Netherlands, 1992; pp 35-54. (b) Nolan, S. P.; Stern, D.; Hedden, D.; Marks, T. J. ACS Symp. Ser. 1990, 428, 159-174. (c) Nolan, S. P.; Stern, D.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 7844-7853. (d) Schock, L. E.; Marks, T. J. J. Am. Chem. Soc. 1988, 110, 7701-7715. (e) Bruno, J. W.; Marks, T. J.; Morss, L. R. J. Am. Chem. Soc. 1983, 105, 6824-6832.
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19. Organic fragment bond enthalpies are from the following: (a) Giller, D.; Kanabus-Kaminska, J. M.; Maccoll, A. J. Mol. Struct. 1988, 163, 125-131. (b) McMillan, D. F.; Golden, D. M. Annu. Rev. Phys. Chem. 1982, 33, 493-532 and references therein. (c) Benson, S. W. Thermochemical Kinetics, 2nd ed.; John Wiley and Sons: New York, 1976; Appendix Tables A.10, A.11, and A.22. (d) Benson, S. W. J. Chem. Educ. 1965, 42, 502-518.
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