Ruthenium NHC Catalyzed Highly Asymmetric Hydrogenation of Benzofurans†
Dr. Nuria Ortega
Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149 Münster (Germany) http://www.uni-muenster.de/Chemie.oc/glorius/index.htm
Search for more papers by this authorSlawomir Urban
Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149 Münster (Germany) http://www.uni-muenster.de/Chemie.oc/glorius/index.htm
Search for more papers by this authorBernhard Beiring
Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149 Münster (Germany) http://www.uni-muenster.de/Chemie.oc/glorius/index.htm
Search for more papers by this authorCorresponding Author
Prof. Dr. Frank Glorius
Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149 Münster (Germany) http://www.uni-muenster.de/Chemie.oc/glorius/index.htm
Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149 Münster (Germany) http://www.uni-muenster.de/Chemie.oc/glorius/index.htmSearch for more papers by this authorDr. Nuria Ortega
Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149 Münster (Germany) http://www.uni-muenster.de/Chemie.oc/glorius/index.htm
Search for more papers by this authorSlawomir Urban
Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149 Münster (Germany) http://www.uni-muenster.de/Chemie.oc/glorius/index.htm
Search for more papers by this authorBernhard Beiring
Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149 Münster (Germany) http://www.uni-muenster.de/Chemie.oc/glorius/index.htm
Search for more papers by this authorCorresponding Author
Prof. Dr. Frank Glorius
Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149 Münster (Germany) http://www.uni-muenster.de/Chemie.oc/glorius/index.htm
Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149 Münster (Germany) http://www.uni-muenster.de/Chemie.oc/glorius/index.htmSearch for more papers by this authorGenerous financial support by the Deutsche Forschungsgemeinschaft (SFB 858) is gratefully acknowledged. The research of F.G. has been supported by the Alfried Krupp Prize for Young University Teachers of the Alfried Krupp von Bohlen und Halbach Foundation. We also thank BASF (Prof. Dr. Klaus Ditrich) for the donation of precious chiral amines (ChiPros). NHC=N-heterocyclic carbene.
Graphical Abstract
H2-O-T! Aromatic O-heterocycles are a challenging substrates for asymmetric hydrogenation (H2). An in situ formed chiral N-heterocyclic carbene (NHC) ruthenium complex allows the high yielding, completely regioselective, and highly asymmetric hydrogenation of substituted benzofurans at room Temperature, giving valuable 2,3-dihydrobenzofurans (see scheme).
Supporting Information
Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors.
| Filename | Description |
|---|---|
| anie_201107811_sm_miscellaneous_information.pdf3.6 MB | miscellaneous_information |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1For Reviews on the hydrogenation of aromatic compounds, see:
- 1aP. J. Dyson, Dalton Trans. 2003, 2964;
- 1bF. Glorius, Org. Biomol. Chem. 2005, 3, 4171;
- 1cY. G. Zhou, Acc. Chem. Res. 2007, 40, 1357;
- 1dR. Kuwano, Heterocycles 2008, 76, 909.
- 2S. Murata, T. Sugimoto, S. Matsuura, Heterocycles 1987, 26, 763.
- 3For selected examples of asymmetric hydrogenations of quinolines, see:
- 3aW. B. Wang, S. M. Lu, P. Y. Yang, X. W. Han, Y. G. Zhou, J. Am. Chem. Soc. 2003, 125, 10536;
- 3bL. Xu, K. H. Lam, J. Ji, J. Wu, Q. H. Fan, W. H. Lo, A. S. C. Chan, Chem. Commun. 2005, 1390;
- 3cM. T. Reetz, X. Li, Chem. Commun. 2006, 2159;
- 3dM. Rueping, A. P. Antonchick, T. Theissmann, Angew. Chem. 2006, 118, 3765;
10.1002/ange.200600191 Google ScholarAngew. Chem. Int. Ed. 2006, 45, 3683;
- 3eW. J. Tang, S. F. Zhu, L. J. Xu, Q. L. Zhou, Q. H. Fan, H. F. Zhou, K. Lam, A. S. C. Chan, Chem. Commun. 2007, 613;
- 3fZ. J. Wang, G. J. Deng, Y. Li, Y. M. He, W. J. Tang, Q. H. Fan, Org. Lett. 2007, 9, 1243;
- 3gZ. W. Li, T. L. Wang, Y. M. He, Z. J. Wang, Q. H. Fan, J. Pan, L. J. Xu, Org. Lett. 2008, 10, 5265;
- 3hN. Mršić, L. Lefort, J. A. F. Boogers, A. J. Minnaard, B. L. Feringa, J. G. de Vries, Adv. Synth. Catal. 2008, 350, 1081;
- 3iM. Rueping, T. Theissmann, S. Raja, J. W. Bats, Adv. Synth. Catal. 2008, 350, 1001;
- 3jS. M. Lu, C. Bolm, Adv. Synth. Catal. 2008, 350, 1101;
- 3kX.-B. Wang, Y.-G. Zhou, J. Org. Chem. 2008, 73, 5640;
- 3lH. F. Zhou, Z. W. Li, Z. J. Wang, T. L. Wang, L. J. Xu, Y. M. He, Q. H. Fan, J. Pan, L. Q. Gu, A. S. C. Chan, Angew. Chem. 2008, 120, 8592; Angew. Chem. Int. Ed. 2008, 47, 8464;
- 3mZ. J. Wang, H. F. Zhou, T. L. Wang, Y. M. He, Q. H. Fan, Green Chem. 2009, 11, 767;
- 3nF.-R. Gou, W. Li, X. Zhang, Y.-M. Liang, Adv. Synth. Catal. 2010, 352, 2441;
- 3oT. Wang, L.-G. Zhuo, Z. Li, F. Chen, Z. Ding, Y. He, Q.-H. Fan, J. Xiang, Z.-X. Yu, A. S. C. Chan, J. Am. Chem. Soc. 2011, 133, 9878. For the use of chiral auxiliaries in the asymmetric heterogeneous hydrogenation of pyridines and quinolines, see:
- 3pF. Glorius, N. Spielkamp, S. Holle, R. Goddard, C. W. Lehmann, Angew. Chem. 2004, 116, 2910; Angew. Chem. Int. Ed. 2004, 43, 2850;
- 3qM. Heitbaum, R. Fröhlich, F. Glorius, Adv. Synth. Catal. 2010, 352, 357.
- 4For selected examples of asymmetric hydrogenations of quinoxalines, see:
- 4aC. Bianchini, P. Barbaro, G. Scapacci, E. Farnetti, M. Graziani, Organometallics 1998, 17, 3308;
- 4bC. Bianchini, P. Barbaro, G. Scapacci, J. Organomet. Chem. 2001, 621, 26;
- 4cC. J. Cobley, J. P. Henschke, Adv. Synth. Catal. 2003, 345, 195;
- 4dJ. P. Henschke, M. J. Burk, C. G. Malan, D. Herzberg, J. A. Peterson, A. J. Wildsmith, C. J. Cobley, G. Casy, Adv. Synth. Catal. 2003, 345, 300;
- 4eL. Qiu, F. Y. Kwong, J. Wu, W. H. Lam, S. Chan, W. Y. Yu, Y. M. Li, R. Guo, Z. Zhou, A. S. C. Chan, J. Am. Chem. Soc. 2006, 128, 5955;
- 4fW. Tang, L. Xu, Q.-H. Fan, J. Wang, B. Fan, Z. Zhou, K.-H. Lam, A. S. C. Chan, Angew. Chem. 2009, 121, 9299; Angew. Chem. Int. Ed. 2009, 48, 9135;
- 4gN. Mršić, T. Jerphagnon, A. J. Minnaard, B. L. Feringa, J. G. de Vries, Adv. Synth. Catal. 2009, 351, 2549;
- 4hM. Rueping, F. Tato, F. R. Schoepke, Chem. Eur. J. 2010, 16, 2688;
- 4iD. Cartigny, T. Nagano, T. Ayad, J. P. Genêt, T. Ohshima, K. Mashima, V. R. Vidala, Adv. Synth. Catal. 2010, 352, 1886;
- 4jQ.-A. Chen, D.-S. Wang, Y.-G. Zhou, Y. Duan, H.-J. Fan, Y. Yang, Z. Zhang, J. Am. Chem. Soc. 2011, 133, 6126.
- 5For selected examples of the asymmetric hydrogenation of indoles see:
- 5aR. Kuwano, K. Sato, T. Kurokawa, D. Karube, Y. Ito, J. Am. Chem. Soc. 2000, 122, 7614;
- 5bR. Kuwano, K. Kaneda, T. Ito, K. Sato, T. Kurokawa, Y. Ito, Org. Lett. 2004, 6, 2213;
- 5cR. Kuwano, M. Kashiwabara, Org. Lett. 2006, 8, 2653;
- 5dN. Mršić, T. Jerphagnon, A. J. Minnaard, B. L. Feringa, J. G. de Vries, Tetrahedron: Asymmetry 2010, 21, 7;
- 5eA. Baeza, A. Pfaltz, Chem. Eur. J. 2010, 16, 2036;
- 5fD.-S. Wang, Q. A. Chen, W. Li, C. B. Yu, Y. G. Zhou, X. Zhang, J. Am. Chem. Soc. 2010, 132, 8909;
- 5gD.-S. Wang, J. Tang, Y.-G. Zhou, M.-W. Chen, Y. Duan, G.-F. Jiang, Chem. Sci. 2011, 2, 803;
- 5hY. Duan, M.-W. Chen, Z.-S. Ye, D.-S. Wang, Q.-A. Chen, Y.-G. Zhou, Chem. Eur. J. 2011, 17, 7193.
- 6For a Review on the recent progress in the synthesis of 2,3-dihydrobenzofurans, see: F. Bertolini, M. Pineschi, Org. Prep. Proced. Int. 2009, 41, 385.
- 7E. Baralt, S. J. Smith, J. Hurwitz, I. T. Horvatz, R. H. Fish, J. Am. Chem. Soc. 1992, 114, 5187.
- 8N. I. Shuikin, I. I. Dmitriev, T. P. Dobrynina, Chem. Abstr. 1941, 35, 2508.
- 9M. Maris, W.-R. Huck, T. Mallat, A. Baiker, J. Catal. 2003, 219, 52.
- 10
- 10aS. Kaiser, S. P. Smidt, A. Pfaltz, Angew. Chem. 2006, 118, 5318;
10.1002/ange.200601529 Google ScholarAngew. Chem. Int. Ed. 2006, 45, 5194. For other pioneering work using Ir/P-N complexes see:
- 10bS. Bell, B. Wüstenberg, S. Kaiser, F. Menges, T. Netscher, A. Pfaltz, Science 2006, 311, 642;
- 10cD. H. Woodmansee, M.-A. Müller, M. Neuburger, A. Pfaltz, Chem. Sci. 2010, 1, 72.
- 11For the use of NHCs as ligands in transition-metal catalysis and organometallic chemistry, see:
- 11aS. P. Nolan, N-Heterocyclic Carbenes in Synthesis, Wiley-VCH, Weinheim, 2006;
10.1002/9783527609451 Google Scholar
- 11bF. Glorius, N-Heterocyclic Carbenes in Transition Metal Catalysis, Springer, Berlin, 2007;
- 11cE. A. B. Kantchev, C. J. O’Brien, M. G. Organ, Angew. Chem. 2007, 119, 2824;
10.1002/ange.200601663 Google ScholarAngew. Chem. Int. Ed. 2007, 46, 2768;
- 11dS. Würtz, F. Glorius, Acc. Chem. Res. 2008, 41, 1523;
- 11eS. Díez-González, N. Marion, S. P. Nolan, Chem. Rev. 2009, 109, 3612. For a Review on the physicochemical properties of NHCs, see:
- 11fT. Dröge, F. Glorius, Angew. Chem. 2010, 122, 7094;
10.1002/ange.201001865 Google ScholarAngew. Chem. Int. Ed. 2010, 49, 6940. For Reviews on NHC organocatalysis, see:
- 11gK. Hirano, I. Piel, F. Glorius, Chem. Lett. 2011, 40, 786;
- 11hA. T. Biju, N. Kuhl, F. Glorius, Acc. Chem. Res. 2011, 44, 1182;
- 11iH. U. Vora, T. Rovis, Aldrichimica Acta 2011, 44, 3;
- 11jV. Nair, R. S. Menon, A. T. Biju, C. R. Sinu, R. R. Paul, A. Jose, V. Sreekumar, Chem. Soc. Rev. 2011, 40, 5336;
- 11kP.-C. Chiang, J. W. Bode, N-Heterocyclic Carbenes as Organic Catalysts in N-Heterocyclic Carbenes: From Laboratory Curiosities to Efficient Synthetic Tools (Ed.: ), Royal Society of Chemistry, London, 2011, p. 399;
- 11lJ. L. Moore, T. Rovis, Top. Curr. Chem. 2010, 291, 77;
- 11mE. M. Phillips, A. Chan, K. A. Scheidt, Aldrichimica Acta 2009, 42, 55;
- 11nD. Enders, O. Niemeier, A. Henseler, Chem. Rev. 2007, 107, 5606.
- 12S. Urban, N. Ortega, F. Glorius, Angew. Chem. 2011, 123, 3887; Angew. Chem. Int. Ed. 2011, 50, 3803.
- 13The catalyst was pre-formed before the hydrogenation reaction: [Ru(cod)(2-methylallyl)2], KOtBu, and the imidazolium salt (3 a or 3 b) were stirred at 70 °C for 12 h in hexane, after which it was added to 1 a and hydrogenation was performed under conditions shown in Table 1.
- 14Yields given are determined by NMR spectroscopy. For more details, see the Supporting Information.
- 15The synthesis of corsifuran A will be reported in due course.
