Palladacycles: Efficient new catalysts for the heck vinylation of aryl halides

Chemistry - A European Journal

Volumn 3, Issue 8, 1997, Pages 1357-1364

  Herrmann, Wolfgang A ^a   Brossmer, Christoph ^b   Reisinger, Claus Peter ^a   Riermeier, Thomas H ^a   Öfele, Karl ^a   Beller, Matthias ^a  

^a TECHNICAL UNIVERSITY OF MUNICH   (Germany)

^b EVONIK INDUSTRIES AG   (Germany)

Author keywords

Aryl halides; Catalysis; Heck reaction; Metallacycles; Palladium

Indexed keywords

EID: 0030767352     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.19970030823     Document Type: Article

References (65)

1. a) R. F. Heck, J. P. Nolley, J. Org. Chem. 1972, 37, 2320;
2. b) T. Mizoroki, K. Mori, A. Ozaki, Bull. Chem. Soc. Jpn 1971, 44, 581.
3. Reviews: a) R. F. Heck, Palladium Reagents in Organic Synthesis, Academic Press, London, 1985; b) R. F. Heck, Vinyl Substitutions with Organopalladium Intermediates in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, Ch. 4.3, p. 833 ff.; c) J. Mulzer, H.-J. Altenbach, M. Braun, K. Krohn, H.-U. Reissig, Organic Synthesis Highlights, VCH, Weinheim, 1991, p. 174 ff; d) A. de Meijere, Angew. Chem. 1994, 106, 2473, Angew. Chem. Int. Ed. Engl. 1994, 33, 2379; e) W. A. Herrmann in Applied Homogeneous Catalysis with Organometallic Compounds, (Eds.: B. Cornils, W. A. Herrmann), VCH Publishers, Weinheim, New York, 1996.
4. Reviews: a) R. F. Heck, Palladium Reagents in Organic Synthesis, Academic Press, London, 1985; b) R. F. Heck, Vinyl Substitutions with Organopalladium Intermediates in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, Ch. 4.3, p. 833 ff.; c) J. Mulzer, H.-J. Altenbach, M. Braun, K. Krohn, H.-U. Reissig, Organic Synthesis Highlights, VCH, Weinheim, 1991, p. 174 ff; d) A. de Meijere, Angew. Chem. 1994, 106, 2473, Angew. Chem. Int. Ed. Engl. 1994, 33, 2379; e) W. A. Herrmann in Applied Homogeneous Catalysis with Organometallic Compounds, (Eds.: B. Cornils, W. A. Herrmann), VCH Publishers, Weinheim, New York, 1996.
5. Reviews: a) R. F. Heck, Palladium Reagents in Organic Synthesis, Academic Press, London, 1985; b) R. F. Heck, Vinyl Substitutions with Organopalladium Intermediates in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, Ch. 4.3, p. 833 ff.; c) J. Mulzer, H.-J. Altenbach, M. Braun, K. Krohn, H.-U. Reissig, Organic Synthesis Highlights, VCH, Weinheim, 1991, p. 174 ff; d) A. de Meijere, Angew. Chem. 1994, 106, 2473, Angew. Chem. Int. Ed. Engl. 1994, 33, 2379; e) W. A. Herrmann in Applied Homogeneous Catalysis with Organometallic Compounds, (Eds.: B. Cornils, W. A. Herrmann), VCH Publishers, Weinheim, New York, 1996.
6. Reviews: a) R. F. Heck, Palladium Reagents in Organic Synthesis, Academic Press, London, 1985; b) R. F. Heck, Vinyl Substitutions with Organopalladium Intermediates in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, Ch. 4.3, p. 833 ff.; c) J. Mulzer, H.-J. Altenbach, M. Braun, K. Krohn, H.-U. Reissig, Organic Synthesis Highlights, VCH, Weinheim, 1991, p. 174 ff; d) A. de Meijere, Angew. Chem. 1994, 106, 2473, Angew. Chem. Int. Ed. Engl. 1994, 33, 2379; e) W. A. Herrmann in Applied Homogeneous Catalysis with Organometallic Compounds, (Eds.: B. Cornils, W. A. Herrmann), VCH Publishers, Weinheim, New York, 1996.
7. Reviews: a) R. F. Heck, Palladium Reagents in Organic Synthesis, Academic Press, London, 1985; b) R. F. Heck, Vinyl Substitutions with Organopalladium Intermediates in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, Ch. 4.3, p. 833 ff.; c) J. Mulzer, H.-J. Altenbach, M. Braun, K. Krohn, H.-U. Reissig, Organic Synthesis Highlights, VCH, Weinheim, 1991, p. 174 ff; d) A. de Meijere, Angew. Chem. 1994, 106, 2473, Angew. Chem. Int. Ed. Engl. 1994, 33, 2379; e) W. A. Herrmann in Applied Homogeneous Catalysis with Organometallic Compounds, (Eds.: B. Cornils, W. A. Herrmann), VCH Publishers, Weinheim, New York, 1996.
8. Reviews: a) R. F. Heck, Palladium Reagents in Organic Synthesis, Academic Press, London, 1985; b) R. F. Heck, Vinyl Substitutions with Organopalladium Intermediates in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, Ch. 4.3, p. 833 ff.; c) J. Mulzer, H.-J. Altenbach, M. Braun, K. Krohn, H.-U. Reissig, Organic Synthesis Highlights, VCH, Weinheim, 1991, p. 174 ff; d) A. de Meijere, Angew. Chem. 1994, 106, 2473, Angew. Chem. Int. Ed. Engl. 1994, 33, 2379; e) W. A. Herrmann in Applied Homogeneous Catalysis with Organometallic Compounds, (Eds.: B. Cornils, W. A. Herrmann), VCH Publishers, Weinheim, New York, 1996.
9. R. R. Bader, P. Baumeister, H.-U. Blaser, Chimia 1996, 50, 99.
10. a) Y. Ben-David, M. Portnoy, M. Gozin, D. Milstein, Organometallics 1992, 11, 1995;
11. b) M. Portnoy, Y. Ben-David, D. Milstein, ibid. 1993, 12, 4734;
12. c) M. Portnoy, D. Milstein, ibid. 1993, 12, 1655;
13. d) M. Portnoy, D. Milstein, ibid. 1993, 12, 1665.
14. Review: a) V. V. Grushin, H. Alper, Chem. Rev. 1994, 94, 1047; b) V. V. Grushin, H. Alper, Organometallics 1993, 12, 1890; c) J. J. Bozell, C. E. Vogt, J. Am. Chem. Soc. 1988, 110, 2655; d) M. T. Reetz, R. Breinbauer, K. Wanninger, Tetrahedron Lett. 1996, 37, 4499-4502.
15. Review: a) V. V. Grushin, H. Alper, Chem. Rev. 1994, 94, 1047; b) V. V. Grushin, H. Alper, Organometallics 1993, 12, 1890; c) J. J. Bozell, C. E. Vogt, J. Am. Chem. Soc. 1988, 110, 2655; d) M. T. Reetz, R. Breinbauer, K. Wanninger, Tetrahedron Lett. 1996, 37, 4499-4502.
16. Review: a) V. V. Grushin, H. Alper, Chem. Rev. 1994, 94, 1047; b) V. V. Grushin, H. Alper, Organometallics 1993, 12, 1890; c) J. J. Bozell, C. E. Vogt, J. Am. Chem. Soc. 1988, 110, 2655; d) M. T. Reetz, R. Breinbauer, K. Wanninger, Tetrahedron Lett. 1996, 37, 4499-4502.
17. Review: a) V. V. Grushin, H. Alper, Chem. Rev. 1994, 94, 1047; b) V. V. Grushin, H. Alper, Organometallics 1993, 12, 1890; c) J. J. Bozell, C. E. Vogt, J. Am. Chem. Soc. 1988, 110, 2655; d) M. T. Reetz, R. Breinbauer, K. Wanninger, Tetrahedron Lett. 1996, 37, 4499-4502.
18. B. A. Patel, C. B. Ziegler, N. A. Cortese, J. E. Plevyak, T. C. Zebovitz, M. Terpko, R. F. Heck, J. Org. Chem. 1977, 42, 3903.
19. S. Hillers, S. Sartori, O. Reiser, J. Am. Chem. Soc. 1996, 118, 2087.
20. H.-U. Blaser, A. Spencer, J. Organomet. Chem. 1982, 233, 267.
21. Preliminary communication: W. A. Herrmann, C. Brossmer, K. Öfele, C.-P. Reisinger, T. Priermeier, M. Beller, H. Fischer, Angew. Chem. 1995, 107, 1989; Angew. Chem. Int. Ed. Engl. 1995, 34, 1844.
22. Preliminary communication: W. A. Herrmann, C. Brossmer, K. Öfele, C.-P. Reisinger, T. Priermeier, M. Beller, H. Fischer, Angew. Chem. 1995, 107, 1989; Angew. Chem. Int. Ed. Engl. 1995, 34, 1844.
23. a) W. A. Herrmann, C. Brossmer, K. Öfele, M. Beller, H. Fischer J. Organomet. Chem. 1995, 491, C1;
24. b) C. Brossmer, Dissertation, Technical University of Munich, 1994.
25. a) A. J. Cheney, B. L. Shaw, J. Chem. Soc. Dalton Trans. 1972, 860;
26. b) A. J. Cheney, B. L. Shaw, ibid. 1972, 754;
27. c) D. F. Gill, B. E. Mann, B. L. Shaw, ibid. 1973, 270.
28. 3 see also: a) E. C. Alyea, J. Malito, J. Organomet. Chem. 1988, 340, 119; b) E. C. Alyea, S.A. Dias, Transition Met. Chem. 1981, 6, 24; c) E. C. Alyea, G. Ferguson, J. Malito, B. L. Ruhl, Organometallics. 1989, 8, 1188.
29. 3 see also: a) E. C. Alyea, J. Malito, J. Organomet. Chem. 1988, 340, 119; b) E. C. Alyea, S.A. Dias, Transition Met. Chem. 1981, 6, 24; c) E. C. Alyea, G. Ferguson, J. Malito, B. L. Ruhl, Organometallics. 1989, 8, 1188.
30. 3 see also: a) E. C. Alyea, J. Malito, J. Organomet. Chem. 1988, 340, 119; b) E. C. Alyea, S.A. Dias, Transition Met. Chem. 1981, 6, 24; c) E. C. Alyea, G. Ferguson, J. Malito, B. L. Ruhl, Organometallics. 1989, 8, 1188.
31. D. Garbe in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A7, 1992, 99.
32. a) C. Amatore, A. Jutand, M. A. M'Barki, Organometallics 1992, 11, 3009;
33. b) F. Ozawa, A. Kubo, T. Hayashi, Chem. Lett. 1992, 2177;
34. c) S. Hiller, S. Saratori, O. Reisier, J. Am. Chem. Soc. 1996, 118, 2077.
35. a) J. P. Collman, L. S. Hegedus, J. R. Norton, R. G. Finke, Principles and Applications of Organotransition Metal Chemistry, University Science Books, Mill Valley, CA (USA), 1987;
36. b) M. Huser, M.-T. Youinou, J. A. Osborn, Angew. Chem. 1989, 101, 1427; Angew. Chem. Int. Ed. Engl. 1989, 28, 1386;
37. b) M. Huser, M.-T. Youinou, J. A. Osborn, Angew. Chem. 1989, 101, 1427; Angew. Chem. Int. Ed. Engl. 1989, 28, 1386;
38. c) P. Fitton, E. A. Rick, J. Organomet. Chem. 1971, 28, 287.
39. Preparative examples: a) M. Catellani, M. C. Fagnola, Angew. Chem. 1994, 106, 2559; Angew. Chem. Int. Ed. Engl. 1994, 33, 2421; b) R. van Asselt, E. Rijnberg, C. J. Elsevier, Organometallics 1994, 13, 706; c) G. Bocelli, M. Catellani, S. Ghelli, J. Organomet. Chem. 1993, 458, C12; d) A. J. Canty, Acc. Chem. Res. 1992, 25, 83.
40. Preparative examples: a) M. Catellani, M. C. Fagnola, Angew. Chem. 1994, 106, 2559; Angew. Chem. Int. Ed. Engl. 1994, 33, 2421; b) R. van Asselt, E. Rijnberg, C. J. Elsevier, Organometallics 1994, 13, 706; c) G. Bocelli, M. Catellani, S. Ghelli, J. Organomet. Chem. 1993, 458, C12; d) A. J. Canty, Acc. Chem. Res. 1992, 25, 83.
41. Preparative examples: a) M. Catellani, M. C. Fagnola, Angew. Chem. 1994, 106, 2559; Angew. Chem. Int. Ed. Engl. 1994, 33, 2421; b) R. van Asselt, E. Rijnberg, C. J. Elsevier, Organometallics 1994, 13, 706; c) G. Bocelli, M. Catellani, S. Ghelli, J. Organomet. Chem. 1993, 458, C12; d) A. J. Canty, Acc. Chem. Res. 1992, 25, 83.
42. Preparative examples: a) M. Catellani, M. C. Fagnola, Angew. Chem. 1994, 106, 2559; Angew. Chem. Int. Ed. Engl. 1994, 33, 2421; b) R. van Asselt, E. Rijnberg, C. J. Elsevier, Organometallics 1994, 13, 706; c) G. Bocelli, M. Catellani, S. Ghelli, J. Organomet. Chem. 1993, 458, C12; d) A. J. Canty, Acc. Chem. Res. 1992, 25, 83.
43. Preparative examples: a) M. Catellani, M. C. Fagnola, Angew. Chem. 1994, 106, 2559; Angew. Chem. Int. Ed. Engl. 1994, 33, 2421; b) R. van Asselt, E. Rijnberg, C. J. Elsevier, Organometallics 1994, 13, 706; c) G. Bocelli, M. Catellani, S. Ghelli, J. Organomet. Chem. 1993, 458, C12; d) A. J. Canty, Acc. Chem. Res. 1992, 25, 83.
44. a) C.-M. Andersson, A. Hallberg, J. Org. Chem. 1987, 52, 3529;
45. b) G. D. Davies, A. Hallberg, Chem. Rev. 1989, 89, 1433.
46. J. H. Rigby, R. C. Hughes, M. J. Heeg, J. Am. Chem. Soc. 1995, 117, 7834.
47. H. A. Dieck, R. F. Heck, J. Am. Chem. Soc. 1974, 96, 1133.
48. For reviews on cyclometallation reactions see: a) A. D. Ryabov, Chem. Rev. 1990, 90, 403; b) V. V. Dunina, O. A. Zalevskaya, V. M. Potapov, Russ. Chem. Rev. 1988, 57, 250.
49. For reviews on cyclometallation reactions see: a) A. D. Ryabov, Chem. Rev. 1990, 90, 403; b) V. V. Dunina, O. A. Zalevskaya, V. M. Potapov, Russ. Chem. Rev. 1988, 57, 250.
50. W. A. Herrmann, C. Brossmer, K. Öfele, M. Beller, H. Fischer, J. Organomet. Chem. 1995, 491, C1.
51. a) W. A. Herrmann, C. Brossmer, T. Priermeier, K. Öfele, J. Organomet. Chem. 1994, 481, 97;
52. b) K.-C. Kong, C.-H. Cheng, J. Am. Chem. Soc. 1991, 113, 6313;
53. c) P. E. Garrou, Chem. Rev. 1985, 85, 171;
54. d) K. Kikukawa, T. Matsuda, J. Organomet. Chem. 1982, 235, 243.
55. 3/DMF. Aryl chlorides and deactivated bromoarenes (e.g. 4-bromoanisole) show only minor reactivity, if any, with these catalyst systems. For original references see: a) T. Jeffrey, Tetrahedron Lett. 1985, 26, 2667; b) T. Jeffrey, J. Chem. Soc. Chem. Commun. 1984, 1287.
56. 3/DMF. Aryl chlorides and deactivated bromoarenes (e.g. 4-bromoanisole) show only minor reactivity, if any, with these catalyst systems. For original references see: a) T. Jeffrey, Tetrahedron Lett. 1985, 26, 2667; b) T. Jeffrey, J. Chem. Soc. Chem. Commun. 1984, 1287.
57. M. Beller, H. Fischer, K. Kühlein, C.-P. Reisinger, W. A. Herrmann, J. Organomet. Chem. 1996, 520, 257.
58. Electrochemical investigations by Amatore et al. revealed an acetato-coordinated anionic bis-(triphenylphosphine)palladium(0) complex as the active species in the oxidative addition of aryl iodides: C. Amatore, E. Carre, A. Jutand, M. A. M'Barki, G. Meyer, Organometallics 1995, 14, 5605.
59. 3 (Pd:P = 1:1) was found to react approximately five times faster than 1a in the Heck coupling of 4-bromobenzaldehyde at 100 °C, but higher temperatures for deactivated substrates led to early precipitation of Pd black. Insufficiently coordinated or "naked" palladium acetate in a 1:1 mixture seems to combine high activity with low stability, so it is only of limited practical use (e.g., aryl iodides).
60. a) R. F. Heck, Pure Appl. Chem. 1978, 50, 691;
61. b) R. F. Heck, Acc. Chem. Res. 1979, 12, 146.
62. C. B. Ziegler, R. F. Heck, J. Org. Chem. 1978, 43, 2941
63. T. Mitsudo, W. Fischetti, R. F. Heck, J. Org. Chem. 1984, 49, 1640.
64. The reported reduction step for amination reactions with palladacycles [J. Louie, J. F. Hartwig, Angew. Chem. 1996, 108, 2531, Angew. Chem. Int. Ed. Engl. 1996, 35, 2339] works with KOtBu combined with a secondary amine as hydride donor. Our investigations, without a secondary amine, demonstrated that KOtBu can deprotonate the benzylic position of the catalyst under typical reaction conditions (100 °C), resulting in the decomposition of the palladacycle. Furthermore, the application of diphenylamine in the amination of bromotoluene with palladacycles works equally well and cannot be explained by the mechanistic features described by Hartwig. Other stoichiometric reactions of substrates with palladacycles, such as olefin insertion into the Pd-C bond, hydrolysis of the Pd-C bond with acetic acid, a Wacker-type reduction with the olefin, or deprotonation of the benzylic methylene group of the catalyst by NaOAc, are not observed.
65. The reported reduction step for amination reactions with palladacycles [J. Louie, J. F. Hartwig, Angew. Chem. 1996, 108, 2531, Angew. Chem. Int. Ed. Engl. 1996, 35, 2339] works with KOtBu combined with a secondary amine as hydride donor. Our investigations, without a secondary amine, demonstrated that KOtBu can deprotonate the benzylic position of the catalyst under typical reaction conditions (100 °C), resulting in the decomposition of the palladacycle. Furthermore, the application of diphenylamine in the amination of bromotoluene with palladacycles works equally well and cannot be explained by the mechanistic features described by Hartwig. Other stoichiometric reactions of substrates with palladacycles, such as olefin insertion into the Pd-C bond, hydrolysis of the Pd-C bond with acetic acid, a Wacker-type reduction with the olefin, or deprotonation of the benzylic methylene group of the catalyst by NaOAc, are not observed.