10.1002/cctc.201800953
ChemCatChem
COMMUNICATION
[4]
a) T. Katsuki, J. Mol. Catal. A: Chem. 1996, 113, 87–107; b) T. Katsuki,
Synlett 2003, 281–297; c) D. A. Valyaev, G. Lavigne, N. Lugan, Coord.
Chem. Rev. 2016, 308, 191–235; d) J. R. Carney, B. R. Dillon, S. P.
Thomas, Eur. J. Org. Chem. 2016, 2016, 3912–3929;
In conclusion, we have demonstrated that aminotriazole
ligands are promising lead structures for the development of
efficient manganese (I) catalyst for transfer hydrogenation of
ketones. Good to excellent yields could be achieved for a large
substrate scope spanning from aromatic ketones to aliphatic
ketones in presence of different functional groups. Iso-propanol
can be used as hydrogen donor together with different bases
including even NaOH as co-catalyst in certain cases. The catalytic
results obtained with a systematic series of ligands suggest an
out-sphere hydrogen transfer involving the amino function as
proton source. Further mechanistic studies are currently ongoing
to elucidate the detailed catalytic cycle.
[5]
[6]
A. Mukherjee, A. Nerush, G. Leitus, L. J.W. Shimon, Y. Ben David, N. A.
Espinosa Jalapa, D. Milstein, J. Am. Chem. Soc. 2016, 138, 4298–4301.
S. Elangovan, C. Topf, S. Fischer, H. Jiao, A. Spannenberg, W.
Baumann, R. Ludwig, K. Junge, M. Beller, J. Am. Chem. Soc. 2016, 138,
8809–8814.
[7]
a) S. Kar, A. Goeppert, J. Kothandaraman, G. K.S. Prakash, ACS Catal.
2017, 7, 6347–6351; b) A. Dubey, L. Nencini, R. R. Fayzullin, C. Nervi,
J. R. Khusnutdinova, ACS Catal. 2017, 7, 3864–3868; c) F. Bertini, M.
Glatz, N. Gorgas, B. Stöger, M. Peruzzini, L. F. Veiros, K. Kirchner, L.
Gonsalvi, Chem. Sci. 2017, 8, 5024–5029; d) A. Kumar, T. Janes, N. A.
Espinosa-Jalapa, D. Milstein, Angew. Chem. Int. Ed. 2018, available
online; DOI 10.1002/anie.201806289; e) A. Kaithal, S. Sen, C. Erken, T.
Weyhermüller, M. Hölscher, C. Werlé, W. Leitner, submitted for
publication.
Experimental Section
[8]
[9]
a) J. Neumann, S. Elangovan, A. Spannenberg, K. Junge, M. Beller,
Chem. Eur. J. 2017, 23, 5410–5413; b) M. Mastalir, M. Glatz, N. Gorgas,
B. Stöger, E. Pittenauer, G. Allmaier, L. F. Veiros, K. Kirchner, Chem.
Eur. J. 2016, 22, 12316–12320; c) S. Elangovan, J. Neumann, J. B.
Sortais, K. Junge, C. Darcel, M. Beller, Nat. Commun. 2016, 7, 1–8;
a) Glatz, M., Stöger, B., Himmelbauer, D., Veiros, L. F. & Kirchner, K.
ACS Catal. 2018, 8, 4009-4016; b) Widegren, M. B. & Clarke, M. L. Org.
Lett. 2018, 20, 2654-2658; c) M. Garbe, K. Junge, S. Walker, Z. Wei, H.
Jiao, A. Spannenberg, S. Bachmann, M. Scalone, M. Beller, Angew.
Chem. Int. Ed. 2017, 56, 11237–11241; d) V. Papa, J. R. Cabrero-
Antonino, E. Alberico, A. Spanneberg, K. Junge, H. Junge, M. Beller,
Chem. Sci. 2017, 8, 3576–3585; e) F. Kallmeier, T. Irrgang, T. Dietel, R.
Kempe, Angew. Chem. Int. Ed. 2016, 55, 11806–11809; f) R. van Putten
et al., Angew. Chem. Int. Ed. 2017, 56, 7531–7534;
General procedure for the catalytic transfer hydrogenation:
Isopropanol (2 mL) was added to a mixture of complex 5 (6.1 mg, 0.015
mmol), considered ketone (0.5 mmol), base (0.003 mmol), and mesitylene
(0.5 mmol, 70 μL). The reaction mixture was stirred at 80 °C for 20 h. After
this time, the reaction was cooled to room temperature. A sample of 0.2
mL of the mixture was added to 0.6 mL of CDCl3, filtered over celite, and
1H-NMR was recorded to determine the yield using the peak of mesitylene
as internal standard.
Acknowledgements
We gratefully acknowledge generous financial supports by the
MPG and the RWTH Aachen University as well as additional
support by the MANGAN project.
[10] a) M. Perez, S. Elangovan, A. Spannenberg, K. Junge, M. Beller,
ChemSusChem 2017, 10, 83–86; b) A. Zirakzadeh, S. R. M. M. de Aguiar,
B. Stöger, M. Widhalm, K. Kirchner, ChemCatChem 2017, 9, 1744–1748;
[11] a) Leitner, W., Kaithal, A. & Markus, H. Angew. Chem. Int. Ed. 2018,
doi:10.1002/anie.201808676; b) Kumar, A., Janes, T., Espinosa-Jalapa,
N. A. & Milstein, D. Angew. Chem. Int. Ed. 2018, 57, 12076-12080 c)
Zubar, V., Lebedev, Y., Azofra, L. M., Cavallo, L., El-Sepelgy, O. &
Rueping, M. Angew. Chem. Int. Ed. 2018, doi:10.1002/anie.201805630.
d) Wei, D., Bruneau-Voisine, A., Valyaev, D. A., Lugan, N. & Sortais, J.-
B. Chem. Commun. 2018, 54, 4302-4305; e) F. Kallmeier, B. Dudziec, T.
Irrgang, R. Kempe, Angew. Chem. Int. Ed. 2017, 56, 7261–7265; f) N.
Deibl, R. Kempe, Angew. Chem. Int. Ed. 2017, 56, 1663–1666; g) M. B.
Widegren, G. J. Harkness, A. M. Z. Slawin, D. B. Cordes, M. L. Clarke,
Angew. Chem. Int. Ed. 2017, 56, 5825–5828; h) A. Kumar, N. A.
Espinosa-Jalapa, G. Leitus, Y. Diskin-Posner, L. Avram, D. Milstein,
Angew. Chem. Int. Ed. 2017, 56, 14992–14996;
Keywords: Catalysis ꔷ Manganese Complexes ꔷ Reduction of
ketones ꔷ Transfer Hydrogenation ꔷ Triazole Ligands
References
[1]
a) P. T. Anastas, J. C. Warner, Green chemistry. Theory and practice
Oxford University Press, Oxford, 1998; b) P. Anastas, B. Han, W. Leitner,
M. Poliakoff, Green Chem. 2016, 18, 12–13; c) R. A. Sheldon, ACS
Sustain. Chem. Eng. 2018, 6, 32–48; d) H. C. Erythropel, J. B.
Zimmerman, T.M. de Winter, L. Petitjean, F. Melnikov, C. H. Lam, A. W.
Lounsbury, K. E. Mellor, N. Z. Janković, Q: Tu, L. N. Pincus, M. M.
Falinski, W. Shi, P. Coish, D. L. Plata, P. T. Anastas, Green Chem. 2018,
20, 1929-1961.
[12] M. Garbe, K. Junge, M. Beller, Eur. J. Org. Chem. 2017, 2017, 4344–
4362.
[13] a) D. Wang, A. Bruneau-Voisine, J.-B. Sortais, Catal. Commun. 2018,
105, 31–36; b) A. Bruneau-Voisine, D. Wang, V. Dorcet, T. Roisnel, C.
Darcel, J.-B. Sortais, Org. Lett. 2017, 19, 3656–3659;
[2]
[3]
a) P. W. N. M. Leeuwen, Homogeneous Catalysis. Understanding the Art,
Kluwer Academic Publishers, Dordrecht, 2004; b) J. F. Hartwig,
Organotransition metal chemistry. From bonding to catalysis, University
Science Books, Sausalito, Calif., 2010; c) B. Cornils, W. A. Herrmann, M.
Beller, R. Paciello, Applied homogeneous catalysis with organometallic
compounds. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2017.
a) A. Correa, O. Garcia Mancheno, C. Bolm, Chem. Soc. Rev. 2008, 37,
1108–1117; b) K. Junge, K. Schroder, M. Beller, Chem. Commun. 2011,
47, 4849–4859; c) L. C. Misal Castro, H. Li, J.-B. Sortais, C. Darcel,
Green Chem. 2015, 17, 2283–2303; d) J. E. Zweig, D. E. Kim, T. R.
Newhouse, Chem. Rev. 2017, 117, 11680–11752; e) S. Z. Tasker, E. A.
Standley, T. F. Jamison, Nature 2014, 509, 299–309; f) G. Evano, N.
Blanchard, M. Toumi, Chem. Rev. 2008, 108, 3054–3131; g) P.
Gandeepan, C.-H. Cheng, Acc. Chem. Res. 2015, 48, 1194–1206;
[14] a) S. Hashiguchi, A. Fujii, J. Takehara, T. Ikariya, R. Noyori, J. Am. Chem.
Soc. 1995, 117, 7562–7563; b) K.-J. Haack, S. Hashiguchi, A. Fujii, T.
Ikariya, R. Noyori, Angew. Chem. Int. Ed. 1997, 36, 285–288;
[15] D. Schweinfurth, L. Hettmanczyk, L. Suntrup, B. Sarkar, Z. Anorg. Allg.
Chem. 2017, 643, 554–584.
[16] M. S. Singh, S. Chowdhury, S. Koley, Tetrahedron 2016, 72, 5257–5283.
[17] a) D. L.J. Broere, R. Plessius, J. Tory, S. Demeshko, B. de Bruin, M. A.
Siegler, F. Hartl, J. I. van der Vlugt, Chem. Eur. J. 2016, 22, 13965–
13975; b) S. Paganelli, M. M. Alam, V. Beghetto, A. Scrivanti, E. Amadio,
M. Bertoldini, U. Matteoli, Appl. Catal., A 2015, 503, 20–25; c) K. Q.
Vuong, M. G. Timerbulatova, M. B. Peterson, M. Bhadbhade, B. A.
Messerle, Dalton Trans. 2013, 42, 14298–14308; d) R. J. Detz, S. A.
Heras, R. de Gelder, P. W. N. M. van Leeuwen, H. Hiemstra, J. N. H.
This article is protected by copyright. All rights reserved.