Chemistry - A European Journal
10.1002/chem.202002777
COMMUNICATION
[
16] L. Winner, W. C. Ewing, K. Geetharani, T. Dellermann, B. Jouppi, T.
reduction of the arene could be due to a direct hydrogen transfer
and indirect via the equilibrium described in supporting
information S3 leading to the formation of hydrogen gas that can
also be transferred to the arene. A deuterium exchange between
deuterium gas and ammonia borane could lead to underestimated
deuterium incorporation which could indicate a favored indirect
transfer hydrogenation mechanism. Finally, to clarify the nature of
the active catalyst, different experiments were conducted which
indicated that the formed rhodium nanoparticles could be the
active catalyst in this transformation (cf. Figures S4-S6 in
Supporting Information).
Kupfer, M. Schäfer, H. Braunschweig, Angew. Chem. Int. Ed. 2018, 57,
1
2275–12279.
[17] Q. Zhou, W. Meng, J. Yang, H. Du, Angew. Chem. Int. Ed. 2018, 57,
2111–12115.
1
[
[
[
[
18] A. Brzozowska, L. M. Azofra, V. Zubar, I. Atodiresei, L. Cavallo, M.
Rueping, O. El-Sepelgy, ACS Catal. 2018, 8, 4103–4109.
19] Y.-P. Zhou, Z. Mo, M.-P. Luecke, M. Driess, Chem. Eur. J. 2018, 24,
4780–4784.
20] F. Wang, O. Planas, J. Cornella, J. Am. Chem. Soc. 2019, 141, 4235–
4240.
21] Q. Zhou, L. Zhang, W. Meng, X. Feng, J. Yang, H. Du, Org. Lett. 2016,
18, 5189–5191.
[22] S. Li, W. Meng, H. Du, Org. Lett. 2017, 19, 2604–2606.
[
23] Y. Han, Z. Wang, R. Xu, W. Zhang, W. Chen, L. Zheng, J. Zhang, J. Luo,
K. Wu, Y. Zhu, C. Chen, Q. Peng, Q. Liu, P. Hu, D. Wang, Y. Li, Angew.
Chem. Int. Ed. 2018, 57, 11262–11266.
Overall, this work describes the catalytic transfer hydrogenation
of benzenoid arenes via a dual mechanism including direct and
indirect hydrogen transfer. Furthermore, this method provides
direct access to various cyclohexane derivatives and saturated
heterocycles, difficult to prepare by other methods, without the
need of syngas and the associated complicated reaction setup or
harsh reaction conditions.
[
[
[
[
24] M. P. Wiesenfeldt, Z. Nairoukh, W. Li, F. Glorius, Science 2017, 357, 908–
912.
25] M. P. Wiesenfeldt, T. Knecht, C. Schlepphorst, F. Glorius, Angew. Chem.
Int. Ed. 2018, 57, 8297–8300.
26] M. Wollenburg, D. Moock, F. Glorius, Angew. Chem. Int. Ed. 2019, 58,
6549–6553.
27] a) Z. Nairoukh, M. Wollenburg, C. Schlepphorst, K. Bergander, F. Glorius,
Nat. Chem. 2019, 11, 264–270; b) Z. Nairoukh, F. Strieth-Kalthoff, K.
Bergander, F. Glorius, Chem. Eur. J. 2020, 26, 6141–6146.
28] a) V. Lavallo, Y. Canac,C. Präsang, B. Donnadieu, G. Bertrand, Angew.
Chem. Int. Ed. 2005, 44, 5705–5709; b) Y. Wei, B. Rao, X. Cong, X. Zeng,
J. Am. Chem. Soc. 2015, 137, 9250–9253.
[
[29] For thorough elucidations of the catalytically active species in the
hydrogenation of arenes using this catalyst, see:
Acknowledgements
a) D. Moock, M. P. Wiesenfeldt, M. Freitag, S. Muratsugu, S. Ikemoto, R.
Knitsch, J. Schneidewind, W. Baumann, A. H. Schäfer, A. Timmer, M.
Tada, M. R. Hansen, F. Glorius, ACS Catal. 2020, 10, 6309–6317; b) B.
L. Tran, J. L. Fulton, J. C. Linehan, M. Balasubramanian, J. A. Lercher, R.
M. Bullock, ACS Catal. 2019, 9, 4106−4114; c) L. Ling, Y. He, X. Zhang,
M. Luo, X. Zeng, Angew. Chem. Int. Ed. 2019, 58, 6554–6558; d) B. L.
Tran, B. L.; J. L. Fulton, J. C. Linehan, J. A. Lercher, R. M. Bullock, ACS
Catal. 2018, 8, 8441–8449. For a recent report on the investigation and
use of rodium clusters in the challenging hydrogenation of N-
heteroarenes, see: e) S. Kim, F. Loose, M. J. Bezdek, X. Wang, P. J.
Chirik, J. Am. Chem. Soc. 2019, 141, 17900–17908.
We thank the European Research Council (ERC Advanced Grant
Agreement no. 788558), the Alexander von Humboldt Foundation
(
(
C.G.), the Alfried Krupp von Bohlen and Hallbach Foundation
A.H.) and the Hans-Jensen-Minerva Foundation (Z.N.) for
generous financial support. The authors also thank Dr. Michael J.
James for helpful discussions, Matthias Freitag, Martin Bühner
(
nanoAnalyticsGmbH) for SEM analysis and Dr. Klaus Bergander
[
30] L. Pitzer, F. Schäfers, F. Glorius, Angew. Chem. Int. Ed. 2019, 58, 8572–
for NMR measurements.
8576.
[
[
31] E. L. Eliel, H. Satici, J. Org. Chem. 1994, 59, 688–689.
32] K. Murugesan, T. Senthamarai, A. S. Alshammari, R. M. Altamimi, C.
Kreyenschulte, M.-M. Pohl, H. Lund, R. V. Jagadeesh, M. Beller, ACS
Catal. 2019, 9, 8581–8591.
Keywords: Organic chemistry • catalysis • transfer
hydrogenation • benzene reduction •
[33] X. Zhang, L. Ling, M. Luo, X. Zeng, Angew. Chem. Int. Ed. 2019, 58,
16785–16789.
[
[
[
[
1] D. Wang, D. Astruc, Chem. Rev. 2015, 115, 6621–6686.
2] E. Baráth, Catalysts 2018, 8, 671–695.
[34] T. M. Maier, S. Sandl, I. G. Shenderovich, A. J. von Wangelin, J. J.
Weigand, R. Wolf, Chem. Eur. J. 2019, 25, 238–245.
3] E. Knoevenagel, B. Bergdolt, Chem. Ber. 1903, 36, 6621–6686.
4] For the transfer hydrogenation reaction of polarized functional groups
such as ketones, aldehydes and nitro groups using rhodium nanoparticles
see: a) A. Serrano-Maldonado, E. Martin, I. Guerrero-Ríos, Eur. J. Inorg.
Chem. 2019, 2863–2870; b) Z. Hu, Y. Ai, L. Liu, J. Zhou, G. Zhang, H. Liu,
X. Liu, Z. Liu, J. Hu, H. bin Sun, Q. Liang, Adv. Synth. Catal. 2019, 361,
3146–3154; c) C. K. P. Neeli, Y. M. Chung, W. S. Ahn, ChemCatChem
2017, 9, 4570–4579; d) J. Zhou, Y. Li, H. Bin Sun, Z. Tang, L. Qi, L. Liu,
Y. Ai, S. Li, Z. Shao, Q. Liang, Green Chem. 2017, 19, 3400–3407; e) N.
R. Guha, D. Bhattacherjee, P. Das, Tetrahedron Lett. 2014, 55, 2912–
2916; f) P. P. Sarmah, D. K. Dutta, Appl. Catal. A Gen. 2014, 470, 355–
360; g) S. Furukawa, Y. Yoshida, T. Komatsu, ACS Catal. 2014, 4, 1441–
1450; h) X. Gao, R. Liu, D. Zhang, M. Wu, T. Cheng, G. Liu, Chem. Eur.
J. 2014, 20, 1515–1519; i) Y. Sun, G. Liu, H. Gu, T. Huang, Y. Zhang, H.
Li, Chem. Commun. 2011, 47, 2583–2585; j) G. Liu, H. Gu, Y. Sun, J.
Long, Y. Xu, H. Li, Adv. Synth. Catal. 2011, 353, 1317–1324.
[5] D. H. A. Boom, A. R. Jupp, J. C. Slootweg, Chem. Eur. J. 2019, 25, 9133–
9
152.
6] X. Yang, L. Zhao, T. Fox, Z.-X. Wang, H. Berke, Angew. Chem. Int. Ed.
010, 49, 2058–2062.
[
2
[7] X. Yang, T. Fox, H. Berke, Tetrahedron 2011, 67, 7121–7127.
[8] X. Yang, T. Fox, H. Berke, Chem. Commun. 2011, 47, 2053–2055.
[9] X. Yang, T. Fox, H. Berke, Org. Biomol. Chem. 2012, 10, 852–860.
[10] W. Xu, H. Fan, G. Wu, P. Chen, New. J. Chem. 2012, 36, 1496–1501.
[11] N. L. Dunn, M. Ha, A. T. Radosevich, J. Am. Chem. Soc. 2012, 134,
1
1330–11333.
12] C. C. Chong, H. Hirao, R. Kinjo, Angew. Chem. Int. Ed. 2014, 53, 3342–
346.
[
3
[13] S. Li, G. Li, W. Meng, H. Du, J. Am. Chem. Soc. 2016, 138, 12956–12962.
[14] S. Fu, N.-Y. Chen, X. Liu, Z. Shao, S.-P. Luo, Q. Liu, J. Am. Chem. Soc.
2
016, 138, 8588–8594.
15] G. Zeng, S. Maeda, T. Taketsugu, S. Sakaki, J. Am. Chem. Soc. 2016,
38, 13481–13484.
[
1
4
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