Highly Efficient Ruthenium-Catalyzed N-Formylation of Amines with H2 and CO2†
Dr. Lei Zhang
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
Search for more papers by this authorDr. Zhaobin Han
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
Search for more papers by this authorXiaoyu Zhao
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
Search for more papers by this authorDr. Zheng Wang
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
Search for more papers by this authorCorresponding Author
Prof. Dr. Kuiling Ding
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)Search for more papers by this authorDr. Lei Zhang
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
Search for more papers by this authorDr. Zhaobin Han
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
Search for more papers by this authorXiaoyu Zhao
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
Search for more papers by this authorDr. Zheng Wang
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
Search for more papers by this authorCorresponding Author
Prof. Dr. Kuiling Ding
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)Search for more papers by this authorWe acknowledge the National Natural Science Foundation of China (grant nos. 91127041, 20421091, 21472215), a special fund from the Chinese Academy of Sciences (XDA07040404), and the Science and Technology Commission of Shanghai Municipality for financial support of this work.
Abstract
A highly efficient catalyst system based on ruthenium-pincer-type complexes has been discovered for N-formylation of various amines with CO2 and H2, thus affording the corresponding formamides with excellent productivity (turnover numbers of up to 1 940 000 in a single batch) and selectivity. Using a simple catalyst recycling protocol, the catalyst was reused for 12 runs in N,N-dimethylformamide production without significant loss of activity, thus demonstrating the potential for practical utilization of this cost-effective process. A one-pot two-step procedure for hydrogenation of CO2 to methanol via the intermediacy of formamide formation has also been developed.
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References
- 1K. Weissermel, H.-J. Arpe, Industrial Organic Chemistry, 3rd ed., Translated by C. R. Lindley, Wiley-VCH, Weinheim, 1997.
- 2
- 2aJ. Muzart, Tetrahedron 2009, 65, 8313;
- 2bS. Ding, N. Jiao, Angew. Chem. Int. Ed. 2012, 51, 9226; Angew. Chem. 2012, 124, 9360.
- 3C. J. Gerack, L. McElwee-White, Molecules 2014, 19, 7689.
- 4“Formamides”: H. Bipp, H. Kieczka in Ullmann′s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2000.
10.1002/14356007.a12_001 Google Scholar
- 5A. Tlili, E. Blondiaux, X. Frogneux, T. Cantat, Green Chem. 2015, 17, 157.
- 6P. Haynes, L. H. Slaugh, J. F. Kohnle, Tetrahedron Lett. 1970, 11, 365.
10.1016/0040-4039(70)80086-7 Google Scholar
- 7
- 7aP. G. Jessop, Y. Hsiao, T. Ikariya, R. Noyori, J. Am. Chem. Soc. 1994, 116, 8851;
- 7bP. G. Jessop, Y. Hsiao, T. Ikariya, R. Noyori, J. Am. Chem. Soc. 1996, 118, 344.
- 8O. Kröcher, R. A. Köppel, A. Baiker, Chem. Commun. 1997, 453.
- 9
- 9aC. Federsel, A. Boddien, R. Jackstell, R. Jennerjahn, P. J. Dyson, R. Scopelliti, G. Laurenczy, M. Beller, Angew. Chem. Int. Ed. 2010, 49, 9777; Angew. Chem. 2010, 122, 9971;
- 9bC. Federsel, C. Ziebart, R. Jackstell, W. Baumann, M. Beller, Chem. Eur. J. 2012, 18, 72;
- 9cC. Ziebart, C. Federsel, P. Anbarasan, R. Jackstell, W. Baumann, A. Spannenberg, M. Beller, J. Am. Chem. Soc. 2012, 134, 20701.
- 10For reviews, see:
- 10aP. G. Jessop, T. Ikariya, R. Noyori, Chem. Rev. 1995, 95, 259;
- 10bW. Leitner, Angew. Chem. Int. Ed. Engl. 1995, 34, 2207; Angew. Chem. 1995, 107, 2391;
- 10cP. G. Jessop, F. Joo, C. C. Tai, Coord. Chem. Rev. 2004, 248, 2425;
- 10dC. Federsel, R. Jackstell, M. Beller, Angew. Chem. Int. Ed. 2010, 49, 6254; Angew. Chem. 2010, 122, 6392.
- 11
- 11aY. N. Li, R. Ma, L. N. He, Z. F. Diao, Catal. Sci. Technol. 2014, 4, 1498;
- 11bC. A. Huff, M. Sanford, J. Am. Chem. Soc. 2011, 133, 18122;
- 11cS. Wesselbaum, T. Stein, J. Klankermayer, W. Leitner, Angew. Chem. Int. Ed. 2012, 51, 7499; Angew. Chem. 2012, 124, 7617;
- 11dN. M. Rezayee, C. A. Huff, M. S. Sanford, J. Am. Chem. Soc. 2015, 137, 1028.
- 12
- 12aY. Li, I. Sorribes, T. Yan, K. Junge, M. Beller, Angew. Chem. Int. Ed. 2013, 52, 12156; Angew. Chem. 2013, 125, 12378;
- 12bK. Beydoun, T. vom Stein, J. Klankermayer, W. Leitner, Angew. Chem. Int. Ed. 2013, 52, 9554; Angew. Chem. 2013, 125, 9733;
- 12cO. Jacquet, X. Frogneux, C. Das Neves Gomes, T. Cantat, Chem. Sci. 2013, 4, 2127.
- 13Selected recent reviews:
- 13a Carbon Dioxide as Chemical Feedstock (Ed.: ), Wiley-VCH, Weinheim, 2010;
10.1002/9783527629916 Google Scholar
- 13bA. Boddien, F. Gärtner, C. Federsel, I. Piras, H. Junge, R. Jackstell, M. Beller in Organic Chemistry: Breakthroughs and Perspectives (Eds.: ), Wiley-VCH, Weinheim, 2012, p. 685;
10.1002/9783527664801.ch18 Google Scholar
- 13cM. Aresta, A. Dibenedetto, A. Angelini, Chem. Rev. 2014, 114, 1709;
- 13dP. H. Dixneuf, Catal. Lett. 2015, 145, 360.
- 14During the preparation of this manuscript, Sanford et al. reported the hydrogenation of carbon dioxide to methanol by tandem catalysis in the presence of dimethylamine and the catalyst 1 b (Ref. [11d]).
- 15
- 15a Organometallic Pincer Chemistry (Eds.: ), Springer, Heidelberg, 2013;
- 15b Ruthenium in Catalysis (Eds.: ), Springer, Heidelberg, 2014.
- 16For recent reviews, see:
- 16aP. A. Dub, T. Ikariya, ACS Catal. 2012, 2, 1718;
- 16bM. L. Clarke, Catal. Sci. Technol. 2012, 2, 2418;
- 16cC. Gunanathan, D. Milstein, Chem. Rev. 2014, 114, 12024–12087;
- 16dA. M. Smith, R. Whyman, Chem. Rev. 2014, 114, 5477.
- 17
- 17aZ. Han, L. Rong, J. Wu, L. Zhang, Z. Wang, K. Ding, Angew. Chem. Int. Ed. 2012, 51, 13041; Angew. Chem. 2012, 124, 13218;
- 17bW. Kuriyama, T. Matsumoto, O. Ogata, Y. Ino, K. Aoki, S. Tanaka, K. Ishida, T. Kobayashi, N. Sayo, T. Saito, Org. Process Res. Dev. 2012, 16, 166;
- 17cD. Spasyuk, D. G. Gusev, Organometallics 2012, 31, 5239;
- 17dD. Spasyuk, S. Smith, D. G. Gusev, Angew. Chem. Int. Ed. 2013, 52, 2538; Angew. Chem. 2013, 125, 2598.
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