"Click" bis-triazoles as neutral C-H⋯anion-acceptor organocatalysts

Chemistry - A European Journal

Volumn 19, Issue 5, 2013, Pages 1581-1585

  Beckendorf, Stephan ^a   Asmus, Sören ^a   Mück Lichtenfeld, Christian ^a   García Mancheño, Olga ^a  

^a UNIVERSITY OF MÜNSTER   (Germany)

Author keywords

alkylation; anion acceptor; click chemistry; NMR spectroscopy; organocatalysis; triazoles

Indexed keywords

ANION ACCEPTOR; ANION-BINDING; CLICK CHEMISTRY; NMR STUDIES; OPTIMAL CATALYSTS; ORGANOCATALYSIS; ORGANOCATALYSTS; TRIAZOLES;

ALKYLATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION KINETICS;

IONS;

ANION; TRIAZOLE DERIVATIVE;

ALKYLATION; ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; CLICK CHEMISTRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY;

ALKYLATION; ANIONS; CATALYSIS; CLICK CHEMISTRY; MAGNETIC RESONANCE SPECTROSCOPY; MOLECULAR STRUCTURE; TRIAZOLES;

EID: 84872705932     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201203360     Document Type: Article

References (71)

1. Supramolecular Chemistry of Anions (Eds.:, A. Bianchi, K. Bowman-James, E. García-España,), Wiley-VCH, Weinheim, 1997
2. Anion Recognition in Supramolecular Chemistry, Vol. 25 of the Series Topics in Heterocyclic Chemistry (Eds:, P. A. Gale, W. Dehaen,), Springer, Berlin, Heidelberg, 2010
3. special issue on supramolecular chemistry of anions: Chem. Soc. Rev. 2010, 10
4. special issue on molecular recognition: Chem. Rev. 1997, 97, 1231-1734.
5. For an excellent review on the close relationship between (thio)urea anion recognition and organocatalysis, see:, Z. Zhang, P. R. Schreiner, Chem. Soc. Rev. 2009, 38, 1187-1198.
6. H. Juwarker, J. M. Lenhardt, D. M. Pham, S. L. Craig, Angew. Chem. 2008, 120, 3800-3803
7. Angew. Chem. Int. Ed. 2008, 47, 3740-3743
8. Y. Li, A. H. Flood, Angew. Chem. 2008, 120, 2689-2692
9. Angew. Chem. Int. Ed. 2008, 47, 2649-2652.
10. Y. Hua, A. H. Flood, Chem. Soc. Rev. 2010, 39, 1262-1271
11. K. P. McDonald, Y. Hua, S. Lee, A. H. Flood, Chem. Commun. 2012, 48, 5065-5075; for other examples, see
12. Q.-Y. Cao, T. Pradhan, S. Kim, J. S. Kim, Org. Lett. 2011, 13, 4386-4389
13. H. Juwarker, J. M. Lenhardt, J. C. Castillo, E. Zhao, S. Krishnamurthy, R. M. Jamiolkowski, K.-H. Kim, S. L. Craig, J. Org. Chem. 2009, 74, 8924-8934.
14. E. Lallana, R. Riguera, E. Fernandez-Megia, Angew. Chem. 2011, 123, 8956-8966
15. Angew. Chem. Int. Ed. 2011, 50, 8794-8804
16. N. Li, W. H. Binder, J. Mater. Chem. 2011, 21, 16717-16743
17. J. E. Hein, V. V. Fokin, Chem. Soc. Rev. 2010, 39, 1302-1315
18. P. M. E. Gramlich, C. T. Wirges, A. Manetto, T. Carell, Angew. Chem. 2008, 120, 8478-8487
19. Angew. Chem. Int. Ed. 2008, 47, 8350-8358
20. W. H. Binder, S. Sachsenhofer, Macromol. Rapid Commun. 2008, 29, 952-981
21. M. Meldal, Macromol. Rapid Commun. 2008, 29, 1016-1051
22. J. A. Johnson, M. G. Finn, J. T. Koberstein, N. J. Turro, Macromol. Rapid Commun. 2008, 29, 1052-1072
23. J.-F. Lutz, Angew. Chem. 2007, 119, 1036-1043
24. Angew. Chem. Int. Ed. 2007, 46, 1018-1025
25. S. Dedola, S. A. Nepogodiev, R. A. Field, Org. Biomol. Chem. 2007, 5, 1006-1017
26. J. E. Moses, A. D. Moorhouse, Chem. Soc. Rev. 2007, 36, 1249-1262
27. V. D. Bock, H. Hiemstra, J. H. van Maarseveen, Eur. J. Org. Chem. 2006, 51-68; for the inital work, see
28. C. W. Tornøe, C. Christensen, M. Meldal, J. Org. Chem. 2002, 67, 3057-3064
29. V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B. Sharpless, Angew. Chem. 2002, 114, 2708-2711
30. Angew. Chem. Int. Ed. 2002, 41, 2596-2599.
31. H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew. Chem. 2001, 113, 2056-2075
32. Angew. Chem. Int. Ed. 2001, 40, 2004-2021.
33. S. Beckendorf, S. Asmus, O. García Mancheño, ChemCatChem 2012, 4, 926-936; for representative examples of chloride binding, see
34. I. T. Raheem, P. S. Thiara, E. A. Peterson, E. N. Jacobsen, J. Am. Chem. Soc. 2007, 129, 13404-13405; carboxylate binding
35. C. K. De, E. G. Klauber, D. J. Seidel, J. Am. Chem. Soc. 2009, 131, 17060-1761; sulfonate binding
36. H. Xu, S. J. Zuend, M. G. Woll, Y. Tao, E. N. Jacobsen, Science 2010, 327, 986-990.
37. J. Y. Shi, C. A. Wang, Z. J. Li, Q. Wang, Y. Zhang, W. Wang, Chem. Eur. J. 2011, 17, 6206-6213
38. E. Alza, S. Sayalero, P. Kasaplar, D. Almaşi, M. A. Pericàs, Chem. Eur. J. 2011, 17, 11585-11595
39. S. L. Jain, A. Modak, A. Bhaumik, Green Chem. 2011, 13, 586-590
40. E. Alza, S. Sayalero, X. C. Cambeiro, R. Martín-Rapún, P. O. Miranda, M. A. Pericàs, Synlett 2011, 464-468
41. I. Mager, K. Zeitler, Org. Lett. 2010, 12, 1480-1483
42. E. Alza, C. Rodríguez-Escrich, S. Sayalero, A. Bastero, M. A. Pericàs, Chem. Eur. J. 2009, 15, 10167-10172
43. E. Alza, M. A. Pericàs, Adv. Synth. Catal. 2009, 351, 3051-3056, and references cited therein; for examples of the introduction of steric bulk close to the catalyst active site, see
44. S. Luo, H. Xu, X. Mi, J. Li, X. Zheng, J.-P. Cheng, J. Org. Chem. 2006, 71, 9244-9247
45. S. Chandrasekhar, B. Tiwari, B. B. Parida, C. R. Reddy, Tetrahedron: Asymmetry 2008, 19, 495-499, and references cited therein.
46. For an example in which the triazole seems to be the principal functionality of the organocatalyst for the aldol reaction, see:, Y.-W. Zhu, W.-B. Yi, C. J. Cai, Fluorine Chem. Rev. 2011, 132, 71-74; for proposed triazole secondary interactions, see
47. S. Chandrasekhar, K. Mallikarjun, G. Pavankumarreddy, K. V. Rao, B. Jagadeesh, Chem. Commun. 2009, 4985-4987
48. D. Font, S. Sayalero, A. Bastero, C. Jimeno, M. A. Pericàs, Org. Lett. 2008, 10, 337-340.
49. A. Bastero, D. Font, M. A. Pericàs, J. Org. Chem. 2007, 72, 2460-2468
50. H. Struthers, T. L. Mindt, R. Schibli, Dalton Trans. 2010, 39, 675-696
51. S. Beckendorf, O. García Mancheño, Synthesis 2012, 44, 2162-2172, and references cited therein.
52. Ar-5 position, previously used by the authors for solubility issues, was exchanged for a (2-methoxypropan-2-yl)acetylene group to maintain the solubility levels and to avoid building up an ion-pair receptor instead of the desired anion acceptor (see, for example:, S. K. Kim, J. L. Sessler, Chem. Soc. Rev. 2010, 39, 3784-3809).
53. In analogy to the known effect on the thiourea catalysts, the introduction of electron-poor 3,5-bis(trifluoromethyl)phenyl groups gives the highest binding capability, most probably due to the enhance of acidity of the C-H bonds at the triazoles and these aromatic units implicated in the anion recognition. Additionally, the effect of the polarization in the BisTri structures on their binding properties is currently under investigation.
54. All calculations were performed with TURBOMOLE: TURBOMOLE V6.3 2011, a development of University of Karlsruhe and Forschungszentrum Karlsruhe GmbH, 1989-2007, TURBOMOLE GmbH, since 2007; available from http://www.turbomole.com.
55. A. D. Becke, Phys. Rev. B 1988, 38, 3098-3100
56. C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789. Correction for dispersion (D3)
57. S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys. 2010, 132, 154104-154123
58. S. Grimme, S. Ehrlich, L. Goerigk, J. Comput. Chem. 2011, 32, 1456-1465
59. def2-TZVP basis set:, F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys. 2005, 7, 3297-3305
60. COSMO solvation model:, A. Klamt, G. Schüürmann, J. Chem. Soc. Perkin Trans. 1 1993, 2, 799-805.
61. For the involvement of the ortho protons in bis(trifluoromethyl)phenyl thiourea catalysts also reported by NMR studies, see:, Z. Zhang, K. M. Lippert, H. Hausmann, M. Kotke, P. R. Schreiner, J. Org. Chem. 2011, 76, 9764-9776.
62. Thermodynamic corrections have been calculated with the SNF program (, J. Neugebauer, M. Reiher, C. Kind, B. A. Hess, J. Comput. Chem. 2002, 23, 895-910) by using gas-phase optimized structures.
63. A toluene/THF (1:1) solvent mixture was used for solubility reasons.
64. 2 a higher K value than in solvents like THF.
65. O. Hernandez, S. K. Chaudhary, R. H. Cox, J. Porter, Tetrahedron Lett. 1981, 22, 1491-1494.
66. G. A. Olah, in Carbocation Chemistry (Eds.:, G. A. Olah, G. K. S. Praksh,), Wiley-Interscience, Hoboken, 2004, pp. 7-41.
67. 8]THF with BisTri3 showed no change in the NMR signals, suggesting no chloride binding with the catalyst.
68. The reaction in the presence of 5, 10, and 20 mol % of BisTri3 was studied. The use of 10 mol % of catalyst was chosen as compromise considering catalytic loading, reaction time, and conversion; see the Supporting Information.
69. In all control experiments without catalyst, no product formation was detected by GC-FID or GC-MS. Only small traces (<1 % yield) were isolated in the case of compound 3 f, which was incompatible to GC analysis.
70. Unfortunately, the NMR-titration method employed for the determination of the binding constant K for the BisTri catalysts cannot be used for the thiourea 4. As was expected, this N-H donor catalyst 4 showed a higher binding affinity to chloride anion, but a clear not 1:1 host/guest binding model (see the Supporting Information). Therefore, an accurate determination of its binding constant K, even at lower host concentrations, cannot be achieved by this approach (mathematic solution with SigmaPlot) and a more complex mathematic treatment is required.
71. -1); see the Supporting Information.