Title: Expanding the Scope of Metal‐Free Catalytic Hydrogenation through Frustrated Lewis Pair Design
Abstract: Angewandte Chemie International EditionVolume 49, Issue 37 p. 6559-6563 Communication Expanding the Scope of Metal-Free Catalytic Hydrogenation through Frustrated Lewis Pair Design† Gábor Erős, Gábor Erős Institute of Biomolecular Chemistry, Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest (Hungary), Fax: (+36) 1438-1145Search for more papers by this authorHasan Mehdi Dr., Hasan Mehdi Dr. Institute of Biomolecular Chemistry, Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest (Hungary), Fax: (+36) 1438-1145Search for more papers by this authorImre Pápai Dr., Imre Pápai Dr. Institute of Structural Chemistry, Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest (Hungary)Search for more papers by this authorTibor András Rokob Dr., Tibor András Rokob Dr. Institute of Structural Chemistry, Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest (Hungary)Search for more papers by this authorPéter Király, Péter Király Institute of Structural Chemistry, Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest (Hungary)Search for more papers by this authorGábor Tárkányi Dr., Gábor Tárkányi Dr. Institute of Structural Chemistry, Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest (Hungary)Search for more papers by this authorTibor Soós Dr., Tibor Soós Dr. [email protected] Institute of Biomolecular Chemistry, Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest (Hungary), Fax: (+36) 1438-1145Search for more papers by this author Gábor Erős, Gábor Erős Institute of Biomolecular Chemistry, Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest (Hungary), Fax: (+36) 1438-1145Search for more papers by this authorHasan Mehdi Dr., Hasan Mehdi Dr. Institute of Biomolecular Chemistry, Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest (Hungary), Fax: (+36) 1438-1145Search for more papers by this authorImre Pápai Dr., Imre Pápai Dr. Institute of Structural Chemistry, Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest (Hungary)Search for more papers by this authorTibor András Rokob Dr., Tibor András Rokob Dr. Institute of Structural Chemistry, Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest (Hungary)Search for more papers by this authorPéter Király, Péter Király Institute of Structural Chemistry, Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest (Hungary)Search for more papers by this authorGábor Tárkányi Dr., Gábor Tárkányi Dr. Institute of Structural Chemistry, Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest (Hungary)Search for more papers by this authorTibor Soós Dr., Tibor Soós Dr. [email protected] Institute of Biomolecular Chemistry, Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest (Hungary), Fax: (+36) 1438-1145Search for more papers by this author First published: 14 June 2010 https://doi.org/10.1002/anie.201001518Citations: 224 † We are grateful for the financial support from the OTKA (grant nos. K-69086, K-60549, and NK-77784) and for the grant GVOP-3.2.1-2004-04-0210/3.0. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Graphical Abstract No metal causes frustration: Based on a conceptual framework, novel frustrated Lewis acid–base catalyst systems with orthogonal reactivity have been developed. Aside from enhanced functional-group tolerance, unique chemoselectivity can be achieved in catalytic metal-free hydrogenations (see scheme). References 1Pioneering work: 1aG. C. Welch, R. R. San Juan, J. D. Masuda, D. W. Stephan, Science 2006, 314, 1124– 1126; most recent review on FLP chemistry: 1bD. W. Stephan, G. Erker, Angew. Chem. 2010, 122, 50– 81; Angew. Chem. Int. Ed. 2010, 49, 46– 76; seminal works and proposals for hydrogen splitting based on non transitions metals: 1cJ. H. Teles, S. Brode, A. Berkessel, J. Am. Chem. Soc. 1998, 120, 1345– 1346; 1dA. Berkessel, T. J. S. Schubert, T. N. Müller, J. Am. Chem. Soc. 2002, 124, 8693– 8698; 1eR. Roesler, W. E. Piers, M. Parvez, J. Organomet. Chem. 2003, 680, 218– 222. 2T. A. Rokob, A. Hamza, A. Stirling, T. Soós, I. Pápai, Angew. Chem. 2008, 120, 2469– 2472; Angew. Chem. Int. Ed. 2008, 47, 2435– 2438. 3Additional theoretical works on the reactivity of FLPs: 3aY. Guo, S. Li, Eur. J. Inorg. Chem. 2008, 2501– 2505; 3bA. Stirling, A. Hamza, T. A. Rokob, I. Pápai, Chem. Commun. 2008, 3148– 3150; 3cY. Guo, S. Li, Inorg. Chem. 2008, 47, 6212– 6219; 3dT. Privalov, Chem. Eur. J. 2009, 15, 1825– 1829; 3eT. Privalov, Dalton Trans. 2009, 1321– 1327; 3fT. A. Rokob, A. Hamza, A. Stirling, I. Pápai, J. Am. Chem. Soc. 2009, 131, 2029– 2036; 3gT. Privalov, Eur. J. Inorg. 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Stephan, Chem. Commun. 2007, 5072– 5074; 4cS. J. Geier, T. M. Gilbert, D. W. Stephan, J. Am. Chem. Soc. 2008, 130, 12632– 12633; 4dD. P. Huber, G. Kehr, K. Bergander, R. Fröhlich, G. Erker, S. Tanino, Y. Ohki, K. Tatsumi, Organometallics 2008, 27, 5279– 5284; 4eH. Wang, R. Fröhlich, G. Kehr, G. Erker, Chem. Commun. 2008, 5966– 5968; 4fM. Ullrich, A. J. Lough, D. W. Stephan, J. Am. Chem. Soc. 2009, 131, 52– 53; 4gA. Ramos, A. J. Lough, D. W. Stephan, Chem. Commun. 2009, 1118– 1120; 4hP. Spies, G. Kehr, K. Bergander, B. Wibbeling, R. Fröhlich, G. Erker, Dalton Trans. 2009, 1534– 1541; 4iC. Jiang, O. Blacque, H. Berke, Organometallics 2009, 28, 5233– 5239. 5Boron–nitrogen Lewis acid–base pairs for cleavage of hydrogen: 5aP. A. Chase, T. Jurca, D. W. Stephan, Chem. Commun. 2008, 1701– 1703; 5bD. Chen, J. Klankermayer, Chem. Commun. 2008, 2130– 2131; 5cV. Sumerin, F. Schulz, M. Nieger, M. Leskelä, T. Repo, B. Rieger, Angew. Chem. 2008, 120, 6090– 6092; Angew. Chem. Int. Ed. 2008, 47, 6001– 6003; 5dV. Sumerin, F. Schulz, M. Atsumi, C. Wang, M. Nieger, M. Leskelä, T. Repo, P. Pyykkö, B. Rieger, J. Am. Chem. Soc. 2008, 130, 14117– 14119; 5eK. V. Axenov, G. Kehr, R. Fröhlich, G. Erker, J. Am. Chem. Soc. 2009, 131, 3454– 3455; 5fS. J. Geier, D. W. Stephan, J. Am. Chem. Soc. 2009, 131, 3476– 3477; 5gV. Sumerin, F. Schulz, M. Nieger, M. Atsumi, C. Wang, M. Leskelä, P. Pyykkö, T. Repo, B. Rieger, J. Organomet. Chem. 2009, 694, 2654– 2660; 5hC. Jiang, O. Blacque, H. Berke, Chem. Commun. 2009, 5518– 5520. 6Boron–carbene Lewis acid–base pairs for cleavage of hydrogen: 6aD. Holschumacher, T. Bannenberg, C. G. Hrib, P. G. Jones, M. Tamm, Angew. Chem. 2008, 120, 7538– 7542; Angew. Chem. Int. Ed. 2008, 47, 7428– 7432; 6bP. A. Chase, D. W. Stephan, Angew. Chem. 2008, 120, 7543– 7547; Angew. Chem. Int. Ed. 2008, 47, 7433– 7437; 6cP. A. Chase, A. L. Gille, T. M. Gilbert, D. W. Stephan, Dalton Trans. 2009, 7179– 7188. 7First FLP-type catalytic hydrogenations: 7aP. A. Chase, G. C. Welch, T. Jurca, D. W. Stephan, Angew. Chem. 2007, 119, 8196– 8199; Angew. Chem. Int. Ed. 2007, 46, 8050– 8053; additional examples: 7bP. Spies, S. Schwendemann, S. Lange, G. Kehr, R. Fröhlich, G. Erker, Angew. Chem. 2008, 120, 7654– 7657; Angew. Chem. Int. Ed. 2008, 47, 7543– 7546; 7cA. E. Ashley, A. L. Thompson, D. O’Hare, Angew. Chem. 2009, 121, 10023– 10027; Angew. Chem. Int. Ed. 2009, 48, 9839– 9843; 7dA. J. M. Miller, J. A. Labinger, J. E. Bercaw, J. Am. Chem. Soc. 2010, 132, 3301– 3303. 8 8aJ. S. J. McCahill, G. C. Welch, D. W. Stephan, Angew. Chem. 2007, 119, 5056– 5059; Angew. Chem. Int. Ed. 2007, 46, 4968– 4971; 8bC. M. Mömming, S. Frömel, G. Kehr, R. Fröhlich, S. Grimme, G. Erker, J. Am. Chem. Soc. 2009, 131, 12280– 12289. 9M. Ullrich, K. S.-H. Seto, A. J. Lough, D. W. Stephan, Chem. Commun. 2009, 2335– 2337. 10 10aM. A. Dureen, D. W. Stephan, J. Am. Chem. Soc. 2009, 131, 8396– 8397; 10bC. Jiang, O. Blacque, H. Berke, Organometallics 2010, 29, 125– 133. 11For reviews on B(C6F5)3 and related fluorinated aryl boranes, see: 11aW. E. Piers, Adv. Organomet. Chem. 2004, 52, 1– 74; 11bG. Erker, Dalton Trans. 2005, 1883– 1890; for the fundamental aspects of the steric and electronic factors in perfluoroaryl borane complexation and catalytic activity, see: 11cP. A. Chase, L. D. Henderson, W. E. Piers, M. Parvez, W. Clegg, M. R. J. Elsegood, Organometallics 2006, 25, 349– 357; 11dD. M. Morrison, W. E. Piers, Org. Lett. 2003, 5, 2857– 2860. 12Related fluorinated boranes were employed by Berke’s group to probe the Lewis acid tuning in intermolecular FLPs, see references [4i, 5h]. Additionally, intramolecular FLPs were developed by Erker’s group (Ref. [4b]) and Repo and Rieger’s groups (Ref. [5d]). Both catalyst systems showed excellent functional-group tolerance, however, their orthogonal reactivity is low[8b] or not yet investigated.[5d] For the only selective hydrogenation of a bulky exotic system with an intramolecular FLP, see: S. Schwendemann, T. A. Tumay, K. V. Axenov, I. Peuser, G. Kehr, R. Fröhlich, G. Erker, Organometallics 2010, 29, 1067– 1069. 13S. A. Cummings, M. Iimura, C. J. Harlan, R. J. Kwaan, I. V. Trieu, J. R. Norton, B. M. Bridgewater, F. Jäkle, A. Sundararaman, M. Tilset, Organometallics 2006, 25, 1565– 1568. 14A similar approach to our concept was probed by Repo, Rieger and co-workers in reference [5g]. Their modified intramolecular ansa-aminoborane system, however, showed poor hydrogen-cleavage activity (the time required for hydrogen splitting changed to one week instead of minutes or hours). 15H. C. Brown, J. Chem. Soc. 1956, 1248– 1268. 16In a preliminary experiment, we verified that substrate 3 a itself could not serve as a Lewis base partner in the hydrogen splitting, thus we can rule out its catalytic contribution in the studied hydrogenation processes. Additionally, the reduced product 4 a proved to be a rather ineffective Lewis base, its autocatalytic contribution is negligible (<2 %). 17See the Supporting Information. 18Besides having less steric demands, amines 13 and 14 are presumably more resistant to a possible hydride abstraction from the α position. For related works, see: 18aF. Focante, P. Mercandelli, A. Sironi, L. Resconi, Coord. Chem. Rev. 2006, 250, 170– 188; 18bN. Millot, C. C. Santini, B. Fenet, J. M. Basset, Eur. J. Inorg. Chem. 2002, 3328– 3335. 19Our efforts to crystallize the zwitterionic product of hydrogen splitting were unsuccessful. 20F. M. Menger, Pure Appl. Chem. 2005, 77, 1873– 1886. 21The systems were investigated at three different levels of computation (M05-2X/6-31G*, M05-2X/6-311++G** and SCS-MP2/cc-pVTZ). Values given in this communication refer to M05-2X/6-311++G** electronic energies, but our conclusions are independent of the applied method (further details are provided in the Supporting Information). 22The free-energy barriers computed with respect to the isolated reactants reflect the same trend (see the Supporting Information). 23The relative basicities of 13 and 8 cannot account for the difference in reactivity towards H2: calculated proton-attachment energies are 243.6 and 243.5 kcal mol−1, respectively. 24A. F. Barrero, E. J. Alvarez-Manzaneda, R. Chahboun, R. Meneses, Synlett 1999, 1663– 1666. Citing Literature 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_201001518_sm_miscellaneous_information.pdf5.8 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. Volume49, Issue37September 3, 2010Pages 6559-6563 ReferencesRelatedInformation
Publication Year: 2010
Publication Date: 2010-06-14
Language: en
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