Full Papers
doi.org/10.1002/cctc.202001937
ChemCatChem
reaction is green and environmentally friendly. This platform
also enables one-shot selective and green syntheses of 1-
methylbenzimidazole using ortho-phenylenediamine (OPDA)
and methanol as coupling partners.
J. M. J. Williams, Dalton Trans. 2009, 753–762; g) M. H. S. A. Hamid, C. L.
Allen, G. W. Lamb, A. C. Maxwell, H. C. Maytum, A. J. A. Watson, J. M. J.
Williams, J. Am. Chem. Soc. 2009, 131, 1766–1774; h) S. Kim, S. H. Hong,
Adv. Synth. Catal. 2017, 359, 798–810; i) Z. Zhang, C. Qiu, Y. Xu, Q. Han,
J. Tang, K. P. Loh, C. Su, Nat. Commun. 2020, 11, 4722.
3] For N-Methylation of amines or nitro compounds using MeOH, see:
a) M. González-Lainez, M. V. Jiménez, V. Passarelli, J. J. Pérez-Torrente,
Catal. Sci. Technol. 2020, 10, 3458–3467; b) V. Goyal, J. Gahtori, A.
Narani, P. Gupta, A. Bordoloi, K. Natte, J. Org. Chem. 2019, 84, 15389–
1
2
3
4
5
6
7
8
9
0
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2
3
4
5
6
7
8
9
0
1
2
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4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
[
Experimental Section
General procedure for N-Methylation of amines. An oven dried
15398; c) J. Wang, J. Wu, Z.-N. Chen, D. Wen, J. Chen, Q. Zheng, X. Xu, T.
Tu, J. Catal. 2020, 389, 337–344; d) B. Paul, S. Shee, K. Chakrabarti, S.
Kundu, ChemSusChem 2017, 10, 2370–2374; e) T. T. Dang, B. Ramalin-
gam, A. M. Seayad, ACS Catal. 2015, 5, 4082–4088; f) B. G. Reed-Berendt,
N. Mast, L. C. Morrill, Eur. J. Org. Chem. 2020, 1136–1140; g) S.
Elangovan, J. Neumann, J.-B. Sortais, K. Junge, C. Darcel, M. Beller, Nat.
Commun. 2016, 7, 12641; h) C. Meng, P. Liu, N. T. Tung, X. Han, F. Li, J.
Org. Chem. 2020, 85, 5815–5824; i) A. Bruneau-Voisine, D. Wang, V.
Dorcet, T. Roisnel, C. Darcel, J.-B. Sortais, J. Catal. 2017, 347, 57–62; j) J.
Neumann, S. Elangovan, A. Spannenberg, K. Junge, M. Beller, Chem. Eur.
J. 2017, 23, 5410–5413; k) Z. Liu, Z. Yang, X. Yu, H. Zhang, B. Yu, Y. Zhao,
Z. Liu, Adv. Synth. Catal. 2017, 359, 4278–4283; l) V. N. Tsarev, Y.
Morioka, J. Caner, Q. Wang, R. Ushimaru, A. Kudo, H. Naka, S. Saito, Org.
Lett. 2015, 17, 2530–2533; m) J. Chen, J. Wu, T. Tu, ACS Sustainable
Chem. Eng. 2017, 5, 11744–11751; n) O. Ogata, H. Nara, M. Fujiwhara, K.
Matsumura, Y. Kayaki, Org. Lett. 2018, 20, 3866–3870; o) D. Wei, O.
Sadek, V. Dorcet, T. Roisnel, C. Darcel, E. Gras, E. Clot, J.-B. Sortais, J.
Catal. 2018, 366, 300–309; p) S. Zhang, J. J. Ibrahim, Y. Yang, Org. Chem.
Front. 2019, 6, 2726–2731; q) L. Wang, H. Neumann, M. Beller, Angew.
Chem. Int. Ed. 2019, 58, 5417–5421; r) H. Zhang, J. Wang, M. Liu, D. Liu,
Appl. Surf. Sci. 2020, 526, 146708; s) L.-M. Wang, K. Jenkinson, A. E. H.
Wheatley, K. Kuwata, S. Saito, H. Naka, ACS Sustainable Chem. Eng. 2018,
6, 15419–15424; t) L.-M. Wang, Y. Morioka, K. Jenkinson, A. E. H. Wheat-
ley, S. Saito, H. Naka, Sci. Rep. 2018, 8, 6931; u) G. Choi, S. H. Hong, ACS
Sustainable Chem. Eng. 2019, 7, 716–723; v) L. Jiang, F. Guo, Y. Wang, J.
Jiang, Y. Duan, Z. Hou, Asian J. Org. Chem. 2019, 8, 2046–2049; w) S.
Huang, X. Hong, H.-Z. Cui, Q. Zhou, Y.-J. Lin, X.-F. Hou, Dalton Trans.
2
5
0 mL ACE® pressure tube was charged with RuCl .xH O (5 mol%,
.18 mg), KOtBu (2 equiv., 112 mg), amine (0.5 mmol), and MeOH
3 2
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(
1
3 mL). The pressure tube was then sealed and allowed to stir at
30°C in oil bath for 24 h. After completion of the reaction, the
pressure tube was cooled to room temperature, and then the
pressure build-up in the tube has been released slowly by losing
the screw cap. The solid catalyst was separated from the reaction
mixture by filtration through filter paper and washed with 3 mL of
ethyl acetate. After evaporating the solvent through rotary
evaporator, the crude mixture was purified by using 60–120 silica
gel column chromatography (ethyl acetate: hexane) to obtain
desired pure product, which was further submitted for NMR
analysis.
Acknowledgements
KN acknowledges the Department of Science and Technology-
Science and Engineering Research Board (DST-SERB), New Delhi
(SRG/2019/002004) for financial support. NS and VG are thankful
to Council of Scientific and Industrial Research (CSIR) New Delhi,
for awarding senior research fellowships (SRF). We gratefully
acknowledge the Analytical Sciences Division of CSIR-IIP for
providing analytical support.
2
019, 48, 5072–5082; x) A. Fu, Q. Liu, M. Jiang, G. Xu, Asian J. Org. Chem.
2019, 8, 487–491; y) S. Huang, X. Hong, H.-Z. Cui, B. Zhan, Z.-M. Li, X.-F.
Hou, Organometallics 2020; z) R. Liang, S. Li, R. Wang, L. Lu, F. Li, Org.
Lett. 2017, 19, 5790–5793; aa) G. Toyooka, A. Tuji, K.-i. Fujita, Synthesis
2
2
018, 50, 4617–4626; ab) L. Xu, X. Li, Y. Zhu, Y. Xiang, New J. Chem.
009, 33, 2051–2054; ac) C.-P. Xu, Z.-H. Xiao, B.-Q. Zhuo, Y.-H. Wang, P.-
Q. Huang, Chem. Commun. 2010, 46, 7834–7836; ad) L. Zhang, Y. Zhang,
Y. Deng, F. Shi, RSC Adv. 2015, 5, 14514–14521; ae) G. Choi, S. H. Hong,
Angew. Chem. Int. Ed. 2018, 57, 6166–6170; Angew. Chem. 2018, 130,
Conflict of Interest
6274–6278; af) A. Lator, S. Gaillard, A. Poater, J-L. Renaud, Org. Lett.
2
018, 20, 5985–5990; ag) K. Polidano, B. D. W. Allen, J. M. J. Williams,
The authors declare no conflict of interest.
L. C. Morrill, ACS Catal. 2018, 8, 6440–6445.
[
[
4] a) J. Chatterjee, C. Gilon, A. Hoffman, H. Kessler, Acc. Chem. Res. 2008,
41, 1331–1342; b) A. F. B. Räder, F. Reichart, M. Weinmüller, H. Kessler,
Keywords: Methanol · RuCl .xH O · N-Methylation · Transfer
3
2
Bioorg. Med. Chem. 2018, 26, 2766–2773; c) J. Chatterjee, F. Rechen-
macher, H. Kessler, Angew. Chem. Int. Ed. 2013, 52, 254–269; Angew.
Chem. 2013, 125, 268–283; d) H. Schönherr, T. Cernak, Angew. Chem. Int.
Ed. 2013, 52, 12256–12267; Angew. Chem. 2013, 125, 12480–12492;
e) E. J. Barreiro, A. E. Kümmerle, C. A. M. Fraga, Chem. Rev. 2011, 111,
5215–5246.
5] a) J. M. Adams, S. Cory, Nature 1975, 255, 28–33; b) S. Ding, N. Jiao,
Angew. Chem. Int. Ed. 2012, 51, 9226–9237; Angew. Chem. 2012, 124,
9360–9371.
[6] a) S. Dabral, T. Schaub, Adv. Synth. Catal. 2019, 361, 223–246; b) Q. Liu,
L. Wu, R. Jackstell, M. Beller, Nat. Commun. 2015, 6, 5933; c) Y. Li, X. Cui,
K. Dong, K. Junge, M. Beller, ACS Catal. 2017, 7, 1077–1086; d) Y. Zhang,
T. Zhang, S. Das, Green Chem. 2020, 22, 1800–1820; e) C. Lu, Z. Qiu, Y.
Zhu, B.-L. Lin, Sci. Bull. 2019, 64, 723–729; f) J. Klankermayer, S.
Wesselbaum, K. Beydoun, W. Leitner, Angew. Chem. Int. Ed. 2016, 55,
7296–7343; Angew. Chem. 2016, 128, 7416–7467; g) S. Das, F. D.
Bobbink, G. Laurenczy, P. J. Dyson, Angew. Chem. Int. Ed. 2014,
53,12876–12879; Angew. Chem. 2014, 126, 13090–13093; h) F. D.
Bobbink, S. Das, P. J. Dyson, Nat. Protoc. 2017, 12, 417–428; i) S. Das,
F. D. Bobbink, S. Bulut, M. Soudani, P. J. Dyson, Chem. Commun. 2016,
52, 2497–2500.
hydrogenation · Pharmaceutical intermediates
[
1] For selected recent reviews and papers, see: a) T. Irrgang, R. Kempe,
Chem. Rev. 2020, 120, 9583–9674; b) M. Pelckmans, T. Renders, S.
Van de Vyver, B. F. Sels, Green Chem. 2017, 19, 5303–5331; c) A. Trow-
bridge, S. M. Walton, M. J. Gaunt, Chem. Rev. 2020, 120, 2613–2692; d) K.
Murugesan, T. Senthamarai, V. G. Chandrashekhar, K. Natte, P. C. J.
Kamer, M. Beller, R. V. Jagadeesh, Chem. Soc. Rev. 2020, 49, 6273–6328;
e) K. Natte, A. Narani, V. Goyal, N. Sarki, R. V. Jagadeesh, Adv. Synth.
Catal. 2020, 23, 5143–5169; f) M. Saad, Curr. Org. Chem. 2019, 23, 1695–
1
737; g) S. Bähn, S. Imm, L. Neubert, M. Zhang, H. Neumann, M. Beller,
ChemCatChem 2011, 3, 1853–1864; h) J. Wang, S. Ye, X. Liu, T.-P. Loh,
ACS Sustainable Chem. Eng. 2020, 8, 16283–16295; i) O. I. Afanasyev, E.
Kuchuk, D. L. Usanov, D. Chusov, Chem. Rev. 2019, 119, 11857–11911;
j) B. Paul, S. Shee, D. Panja, K. Chakrabarti, S. Kundu, ACS Catal. 2018, 8,
2890–2896.
[
2] a) B. G. Reed-Berendt, K. Polidano, L. C. Morrill, Org. Biomol. Chem. 2019,
1
7, 1595–1607; b) K.-i. Shimizu, Catal. Sci. Technol. 2015, 5, 1412–1427;
c) A. Corma, J. Navas, M. J. Sabater, Chem. Rev. 2018, 118, 1410–1459;
d) T. Irrgang, R. Kempe, Chem. Rev. 2019, 119, 2524–2549; e) F. Shi, X.
Cui, in Catalytic Amination for N-Alkyl Amine Synthesis (Eds.: F. Shi, X.
Cui), Academic Press, 2018, pp. 1–58; f) T. D. Nixon, M. K. Whittlesey,
[7] a) K. Natte, H. Neumann, R. V. Jagadeesh, M. Beller, Nat. Commun. 2017,
8, 1344; b) H. Wang, Y. Huang, X. Dai, F. Shi, Chem. Commun. 2017, 53,
5542–5545; c) H. Wang, H. Yuan, B. Yang, X. Dai, S. Xu, F. Shi, ACS Catal.
2018, 8, 3943–3949; d) X. Dong, Z. Wang, Y. Yuan, Y. Yang, J. Catal.
ChemCatChem 2021, 13, 1722–1729
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