Heterogeneous versus homogeneous palladium catalysts for ligandless Mizoroki-Heck reactions: A comparison of batch/microwave and continuous-flow processing

Chemistry - A European Journal

Volumn 15, Issue 4, 2009, Pages 1001-1010

  Glasnov, Toma N ^a   Findenig, Silvia ^a   Kappe, C Oliver ^a  

^a UNIVERSITY OF GRAZ   (Austria)

Author keywords

Cross coupling; Flow chemistry; Heterogeneous catalysis; Microwave assisted reactions nanoparticles; Reaction mechanisms

Indexed keywords

BROMINE COMPOUNDS; CATALYSIS; CATALYSTS; COUPLINGS; ESTERS; FOURIER TRANSFORMS; LEACHING; MICROWAVES; NANOPARTICLES; SUGAR (SUCROSE); TRANSITION METALS;

CROSS-COUPLING; FLOW CHEMISTRY; HETEROGENEOUS CATALYSIS; MICROWAVE-ASSISTED REACTIONS NANOPARTICLES; REACTION MECHANISMS;

PALLADIUM;

EID: 58449122729     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200802200     Document Type: Article

References (122)

1. a) Transition Metals for Organic Synthesis, 2nd ed. (Eds.: M. Beller, C. Bolm), Wiley-VCH. Weinheim, 2004;
2. b) Metal-Catalyzed Cross-Coupling Reactions, Vol. 1-2, 2nd ed. (Eds.: A. deMeijere, F. Diederich), Wiley-VCH, Weinheim, 2004;
3. c) M. Beller, A. Zapf in Handbook of Organopalladium Chemistry for Organic Synthesis, Vol. 1 (Ed.: E.-I. Negishi). Wiley, New York. 2002, pp. 1209-1222.
4. a) I. Beletskaya, A. Cheprakov, Chem. Rev. 2000, 100, 3009;
5. b) V. Farina, Adv. Synth. Catal. 2004, 346, 1553;
6. c) A. de Meijere, F. Diederich. Metal-Catalysed Cross-Coupling Reactions, 2nd ed., Wiley-VCH, Weinheim, 2004;
7. d) J. Tsuji, Palladium Reagents and Catalysts-New Perspectives for the 21st Century, Wiley, New York, 2004.
8. a) L. Yin, J. Liebscher, Chem. Rev. 2007, 107, 133, and references therein;
9. b) V. Polshettiwar, A. Molnár, Tetrahedron 2007, 63, 6949.
10. a) D. Schils, F. Stappers, G. Solberghe, R. van Heck, M. Coppens, D. Van den Heuvel, P. van der Donck, T. Callewaert, F. Meeussen, E. De Bie, K. Eersels, E. Schouleden, Org. Process Res Dev. 2008, 12, 530, and references therein;
11. b) J. G. deVries, Can. J. Chem. 2001, 79, 1086.
12. For general reviews on microwave-assisted transilion-metal catalysis, see: a) P. Appukkuttan, E. van der Eycken, Eur. J. Org. Chem. 2008, 1133;
13. b) P. Nilsson, K. Olofsson, M. Larhed, Top. Curr. Chem. 2006, 266, 103;
14. c) N. E. Leadbeater, Chem. Commun. 2005, 2881;
15. d) C. O. Kappe, Angew. Chem. 2004, 116, 6408:
16. Angew. Chem. Int. Ed. 2004, 43, 6250;
17. e) M. Larhed, C. Moberg, A. Hallberg, Acc Chem. Res 2002, 35, 717.
18. B. Desai, C. O. Kappe, Top. Curr. Chem. 2004, 242, 177.
19. a) M. G. Organ, S. Mayer, F. Lepifre, B. N'Zemba, Mol. Diversity 2003, 7, 211;
20. b) G. Palmisano, W. Bonrath, L. Boffa, D. Garella, A. Barge, G. Cravotto. Adv. Synth. Catal. 2007, 349, 2338;
21. c) X. Xie, J. Lu, B. Chen, J. Han, X. She, X. Pan, Tetrahedron Lett. 2004, 45, 809.
22. R. K. Arvela, N. E. Leadbeater, Org. Lett. 2005, 7, 2101.
23. A. Stadler, B. H. Yousefi, D. Dallinger, P. Walla, E. van der Eycken, N. Kaval, C. O. Kappe, Org. Process Res. Dev. 2003, 7, 707.
24. a) M. S. Pillai, A. Wali, S. Satish, US Patent 2003 100625, 2003;
25. b) P. He, S. J. Haswell, P. D. I. Fletcher, Appl. Catal. A 2004, 274, 111.
26. I. R. Baxendale, C. M. Griffith-Jones, S.V. Ley, G. K. Tranmer, Chem. Eur. J. 2006, 12, 4407.
27. a) A. K. Sharma, J. K. Gowdahalli, S. Amin, J. Org. Chem. 2007, 72, 8987;
28. b) J. Gil-Moltó, S. Karlström, C. Najera. Tetrahedron 2005. 61, 12168.
29. C. Schmöger, T. Szuppa, A. Tied, F. Schneider, A. Stolle, B. Ondruschka. ChemSusChem 2008, 1, 339.
30. a) G. Shore, S. Morin, M. G. Organ, Angew. Chem. 2006, 118, 2827;
31. Angew. Chem. Int. Ed. 2006, 45, 2761;
32. b) E. Comer, M. G. Organ, J. Am. Chem. Soc. 2005, 127, 8160;
33. c) C. Valente, S. Baglione, D. Candito, C.J. O'Brien, M. G. Organ, Chem. Commun. 2008, 735;
34. d) G. Shore, S. Morin, D. Mallik, M. G. Organ, Chem. Eur. J. 2008, 14, 1351.
35. a) B. M. Choudary, S. Madhi, N. S. Chowdari, M. L. Kanlam, B. Sreedhar, J. Am. Chem. Soc. 2002, 124, 14127;
36. b) K. Mennecke, R. Cecilia, T. N. Glasnov, S. Gruhl, C. Vogl, A. Feldhoff, M. A. L. Vargas, C. O. Kappe, U. Kunz, A. Kirschning, Adv. Synth. Catal. 2008, 350, 717;
37. c) A. Barau, V. Budarin, A. Caragheorgheopol, R. Luque, D. J. Macquarrie, A. Prelle, V. S. Teodorescu, M. Zaharescu, Catal. Lett. 2008, 124, 204;
38. d) J. Demel, S.-E. Park, J. Čejka, P. Štěpnič ka, Catal. Today 2008, 132, 63.
39. B. H. Lipshutz, B. A. Frieman, C.-T. Lee, A. Lower, D.M. Nihan, B. R. Taft, Chem. Asian J. 2006, 1, 417.
40. a) T. A. Butler, E. C. Swift, B. H. Lipshutz, Org. Biomol. Chem. 2008, 6, 19;
41. b) B. H. Lipshutz, T. Butler, E. Swift, Org. Lett. 2008, 10, 697.
42. B. H. Lipshutz, J. B. Unger, B. R. Taft, Org. Lett. 2007, 9, 1089.
43. a) U. Kazmaier, S. Hähn, T. D. Weiss, R. Kautenburger, W. F. Maier. Synlett 2007, 2579;
44. b) S. P. Andrews, A. F. Stepan, H. Tanaka, S. V. Ley, M. D. Smith, Adv. Synth. Catal. 2005, 347, 647.
45. a) D. R. Baghurst, D. M. P. Mingos, Chem. Soc. Rev. 1991, 20, 1
46. b) C. Gabriel, S. Gabriel, E. H. Grant, B. S. Halstead, D. M. P. Mingos, Chem. Soc. Rev. 1998, 27, 213;
47. c) M. Gupta, E. Wong Wei Leong. Microwaves and Metals, Wiley, New York, 2007.
48. T. Razzaq, J. M. Kremsner, C. O. Kappe, J. Org. Chem. 2008, 73, 6321; see in particular the Supporting Information, Figure S14 and S15.
49. For examples of selective heating of Pd/C catalysts using microwave irradiation in hydrogenation reactions, see: a) G. S. Vanier, Synlett 2007, 0131;
50. b) E. Heller, W. Lautenschläger, U. Holzgrabe, Tetrahedron Lett. 2005, 46, 1247;
51. c) A. N. Parvulescu, E. van der Eycken, P. A. Jacobs, D. E. De Vos. J. Catal. 2008, 255, 206.
52. J. D. Moseley, P. Lenden, M. Lockwood, K. Ruda, J. -P-Sherlock, A. D. Thomson, J. P. Gilday, Org. Process Res. Dev. 2008, 12, 30, and references therein.
53. For reviews on microwave-assisted continuous-flow processing, see: a) I. R. Baxendale, J. J. Hayward, S. L. Ley, Comb. Chem. High Throughput Screening 2007, 10, 802;
54. b) T. N. Glasnov, C. O. Kappe, Macromol. Rapid Commun. 2007, 28, 395;
55. c) See also: B. K. Singh, N. Kaval, S. Tomar, E. van der Eycken, V. S. Parmar, Org. Process Res. Dev. 2008, 12, 468.
56. a) D. Williams, G. Bradley, H. Lombard. C. W. Holzapfel, Synth. Commun. 2001, 31, 2077;
57. b) L. J. Goossen, J. Paetzold, Angew. Chem. 2002, 114, 1285;
58. Angew. Chem. Int. Ed. 2002, 41, 1237;
59. c) G. K. Datta, K. S. A. Vallin, M. Larhed, Mol. Diversity 2003, 7, 107;
60. d) M. Mayr, M. R. Buchmeister. Macromol Rap. Commun. 2004, 25, 231;
61. e) Ai-E. Wang, J.-H. Xie, L.-X. Wang, Q.-L. Zhoe, Tetrahedron 2005, 61, 259.
62. a) R. S. Dubbaka, P. Vogel, Chem. Eur. J. 2005, 11, 2633;
63. b) X. Cui, Z. Li, C.-Z. Tao, Y. Xu, J. Li, L. Liu, Q.-X. Guo, Org. Lett. 2006, 8, 2467;
64. c) R. S. Dubbaka, D. Zhao, Z. Fei, C. M. R. Volla, P. J. Dyson, P. Vogel, Synlett 2006, 3155;
65. d) X. Cui, Y. Zhou, N. Wang, L. Leiu, Q.-X. Guo, Tetrahedron Lett. 2007, 48, 163;
66. e) X. Cui, J. Li, L. Liu, Q.-X. Guo, Chin. Chem. Lett. 2007, 18. 625;
67. f) X. Cui, J. Li, Z.-P. Zhang, Y. Fu, L. Liu, Q.-X. Guo, J. Org. Chem. 2007, 72, 9342.
68. a) R. G. Heideneich, K. Köhler, J. G. E. Krauter, J. Ketsch, Synlett 2002, 1118;
69. b) K. Köhler, R. G. Heidereich, J. G. E. Krauter, J. Pietsch, Chem. Eur. J. 2002, 8, 622;
70. c) R. G. Heideneich, J. G. E. Krauter, J. Pietsch K. Köhler, Mol. Catal. A 2002, 182, 499.
71. T.Jeffrey, J. Chem. Soc. Chem. Commun. 1984, 1287.
72. a) M. Hosseini, N. Stiasni, V. Barbieri, C. O. Kappe, J. Org. Chem. 2007, 72, 1417;
73. b) M. A. Herrero, J. M. Kremsner, C. O. Kappe, J. Org. Chem. 2008, 73. 36.
74. a) B. L. Hayes, M. J. Collins, Jr., World Patent 2004, WO 04002617;
75. b) B. L. Hayes, Aldrichimica Acta 2004, 37, 66.
76. a) B. K. Singh, P. Appukkuttan, S. Claerhout, V. S. Parmar. E. van der Eycken, Org. Lett. 2006, 8, 1863;
77. b) P. Appukkuttan, M. Husain, R. K. Gupta, V. S. Parmar, E. van der Eycken. Synlett 2006, 1491;
78. c) B. Singh, V. P. Mehta, V. S. Parmar, E. van der Eycken, Org. Biomol. Chem. 2007, 5, 2962.
79. The selective heating of metal particles under microwave condilions is a complex phenomenon depending on the type of support, particle size (surface-to-volume ratio), electromagnetic field strength (power density), and a variety of other factors; for more details, see: R. Cecilia, U. Kunz. T. Turek, Chem. Eng. Process. 2007, 46, 870, and references therein.
80. For selected reviews on continuous-flow processing in organic synthesis, see: a) G. Jas, A. Kirschning, Chem. Eur. J. 2003, 9, 5708;
81. b) P. Watts, S. J. Haswell, Drug Discovery Today 2003, 8, 586;
82. c) I. R. Baxendale, M. R. Pitts, Chim. Oggi 2006, 24, 41;
83. d) A. Kirschning, W. Solodenko, K. Mennecke, Chem. Eur. J. 2006, 12, 5972;
84. e) A. Chighine, G. Sechi, M. Bradley, Drug Discovery Today 2007, 12, 459;
85. f) B. Ahmed-Omer, J. C. Brandt, T. Wirth, Org. Biomol. Chem. 2007, 5, 733;
86. g) C. Wiles, P. Watts. Eur. J. Org. Chem. 2008, 1655.
87. For closely related Mizoroki-Heck reactions in continuous-flow format using immobilized Pd species, see: a) N. Nikbin, M. Ladlow, S. V. Ley, Org. Process Res Dev. 2007, 11, 458 (monolithic nanoparlicles);
88. b) K. Mennecke, W. Solodenko, A. Kirschning, Synthesis 2008, 1589 (immobilized palladacycles);
89. c) N. Karbass, V. Sans, E. Garcia-Verdugo, M. I. Burguele, S. V. Luis, Chem. Commun. 2006, 3095 (immobilized Pd catalysts on monolithic polymers/ionic liquid fragments);
90. d) W. Solodenko, H. Wen, S. Leue, F. Stuhlmann, G. Sourkouni-Argirusi, G. Jas, H. Schoenefeld, U. Kunz, A. Kirschning, Eur. J. Org. Chem. 2004, 3601 (monolithic nanoparticles); e) See also reference [14d].
91. For a detailed description, see: C. Csajági, B. Borcsek. K. Niesz, I. Kovács, Z. Székelyhidi, Z. Bajko. L. Ürge. F. Darvas. Org. Lett. 2008, 10, 1589.
92. The X-Cube and X-Cube Flash product series are available from Thales Nanotechnology Inc. (Budapest. Hungary. For further information, please refer to http://www.thalesnano.com.
93. In fact, each portion of the reaction mixture passing through the microchannels formed by the packed Pd/C catalyst inside the cylindrical cartridge is exposed to stoichiometric amounts of the catalyst. In flow format, the TON of the "catalyst" is therefore dependent on how much material is actually processed through the catalyst cartridge. For the Mizoroki-Heck reaction of la on a 0.65 mmol scale the formal TON is only 6.
94. a) C.-M. Andersson, A. Hallberg, G. D. Davis, Jr., J. Org. Chem. 1987, 52, 3529;
95. b) K. S. A. Vallin, M. Larhed, A. Hallberg, J. Org. Chem. 2001, 66. 4340.
96. a) L. Djakovitch, M. Wagner, C. G. Hartung, M. Beller. K. Köhler, J. Mol. Catal. A 2004, 219, 121;
97. b) F. Zhao, M. Arai, React. Kinet. Catal. Lett. 2004, 81, 281.
98. The amount of Pd in a fresh sample of the commercially available (Aldrich 643181-10G) Degussa Pd/C catalyst (E 104 CA/W 5% Pd) was determined by ICP-MS analysis. The dry catalyst (20% determined water content) has a loading of 4.8% Pd. A 60×4 mm i.d. X-Cube catalyst cartridge filled with 310 mg of the (wet) catalyst therefore contains 12 mg of Pd.
99. For a critical review, see: N. T. S. Phan, M. vanderSluys. C. W. Jones. Adv. Synth. Catal. 2006, 348, 609.
100. For other key references, see: a) A. Biffis, M. Zecca, M. Basato, J. Mol. Catal. A 2001, 173, 249;
101. b) D. Astruc, F. Lu, J. R. Aranzaes, Angew. Chem. 2005, 117. 8062;
102. Angew. Chem. Int. Ed. 2005, 44, 7852;
103. c) J. G. de Vries. Dalton Trans. 2006, 421;
104. d) D. Astruc, Inorg. Chem. 2007, 46, 1884;
105. e) A. M. Trzeciak, J.J. Ziółkowski, Coord. Chem. Rev. 2007, 251, 1281;
106. f) A. Svennebring, P. J. R. Sjoeberg, M. Larhed, P. Nilsson, Tetrahedron 2008, 64, 1808.
107. a) I. W. Davies, L. Matty, D. L. Hughes, P. J. Reider, J. Am. Chem. Soc. 2001, 123, 10139;
108. b) M. Parisien, D. Valette, K. Fagnou, J. Org. Chem. 2005, 70, 7578;
109. c) C. S. Consorti, F. R. Flores, J. Dupont, J. Am. Chem. Soc. 2005, 127, 12054;
110. d) J. M. Richardson, C. W. Christopher, Adv. Synth. Catal. 2006, 348, 1207.
111. Leaching effects in continuous-flow Mizoroki-Heck reactions involving immobilized forms of Pd have been previously observed (ref. [34]). In some cases the leached metal can be efficiently removed online by the use of scavenger resins (ref. [34a]). In other instances the support itself (e.g. poly(vinylpyridine)) has been demonstrated to be able to recapture the Pd metal to some extent (ref. [34b]).
112. If the leaching observed for the specific preparation of Pd/C in Mizoroki-Heck chemistry under flow conditions is a general phenomenon also valid for other immobilized Pd species and/or other transition-metal-catalyzed transformations will be the subject of further investigations.
113. For recent examples of microwave-assisted Mizoroki-Heck reactions using ligandless Pd, see: a) R. K. Arvela. N. E. Leadbeater, J. Org. Chem. 2005, 70, 1786;
114. b) R. K. Arvela, N. E. Leadbeater, M. J. Collins, Tetrahedron 2005, 61. 9349;
115. c) M. D. Bowman, J. L. Holcomb, C. M. Kormos, N. E. Leadbeater, V. A. Williams, Org. Process Res. Dev. 2008, 12, 41;
116. d) M. D. Bowman, J. R. Schmink, C. M. McGowan, C. M. Kormos, N. E. Leadbeater, Org. Process Res. Dev. 2008, 12, 1078;
117. e) J. D. Moseley, E. K. Woodman, Org. Process Res. Dev. 2008, 12, 967. See also ref. [7b].
118. For Mizoroki-Heck reactions performed in a microfluidic device, see: a) B. Ahmed, D. Barrow, T. Wirth, Adv. Synth. Catal. 2006, 348, 1043;
119. b) S. Liu, T. Fukuyama, M. Sato, I. Ryu, Org. Process Res. Dev. 2004, 8, 477.
120. M. T. Reetz, J. G. de Vries, Chem. Commun. 2004, 1559. and references therein: see also references [41] and [42].
121. A. Hinchcliffe, C. Hughes, D. A. Pears, M. R. Pitts, Org. Process Res. Dev. 2007, 11, 477; see also reference [44].
122. Q. Yao, E. P. Kinney, C. Zheng, Org. Lett. 2004, 6, 2997.