10.1002/cctc.201801039
ChemCatChem
FULL PAPER
Z
4
Goodness-of-fit on F2
1.153
Density (calcd), Mg/m3
Absorption coefficient, mm-1
F(000)
Crystal size, mm3
Theta range for data collection ()
Index ranges
1.377
Final R indices [I>2sigma(I)]
R1 = 0.0979, wR2 =
0.2105
0.692
R indices (all data)
R1 = 0.1381, wR2 =
0.2354
3104
0.960 x 0.790 x 0.190
1.778 to 25.249
-26<=h<=26, -
15<=k<=13, -32<=l<=33
60653
Acknowledgements
Reflections collected
Independent reflections
Completeness to
Absorption correction
Max. and min. transmission
Refinement method
13172 [R(int) = 0.0730]
99.7
GIN thanks NSERC for generous financial support. We thanks Dr.
Liqun Qiu for the help with GC-MS analysis.
SADABS, Bruker (2003)
0.5994 and 0.5994
Full-matrix least-squares
Keywords: transfer hydrogenation • ruthenium catalyst • ester • nitrile
• heterocycle
2
on F
Data / restraints / parameters
13172 / 597 / 812
[1]
[2]
D. Wang, D. Astruc, Chem. Rev. 2015, 115, 6621−6686.
B. Grotjahn, S. Van, D. Combs, D.A. Lev, C. Schneider, M. Rideout, C.
Meyer, G. Hernandez, L. Mejorado, J. Org. Chem. 2002, 67, 9200-
9209; c) D. B. Grotjahn, D. Combs, S. Van, G. Aguirre, F. Ortega,
Inorg. Chem. 2000, 39, 2080-2086.
a) Noyori, R.; Hashiguchi, S. Acc. Chem. Res. 1997, 30, 97. b)
Clapham, S. E.; Hadzovic, A.; Morris, R. H. Coord. Chem. Rev. 2004,
248, 2201. c) Fujita, K. –H.; Yamaguchi, R. SYNLETT, 2005, 4, 560. d)
Gladiali, S.; Alberico, E. Chem. Soc. Rev. 2006, 35, 226. e) Ikariya, T.;
Blacker, J. Acc. Chem. Res. 2007, 40, 1300. (f) Baratta, W.; Rigo, P.
Eur. J. Inorg. Chem. 2008, 4041. g) Morris, R. H.; Chem. Soc. Rev.
2009, 38, 2282. h) R. Malacea, R. Poli, E. Manoury, Coord. Chem. Rev.
2010, 254, 729. i) Fukuzumi, S.; Suenobu, T. Dalton Trans. 2013, 42,
18. j) Sues, P. E.; Demmans, K. Z.; Morris, R. H. Dalton Trans. 2014,
43, 7650. k) J. S. Cha, Org. Proc. Develop. 2006, 10, 1032-1053.
a) S. Horn, C. Gandolfi, M. Albrecht, Eur. J. Inorg. Chem. 2011, 2863–
2868; b) E. Mizushima, M. Yamaguchi, T. Yamagishi, J. Mol. Catal. A
1999, 148, 69– 75.
a) S. H. Lee, G. I. Nikonov, ChemCatChem, 2015, 7, 107-113. b) V. H.
Mai, G. I. Nikonov, Organometallics, 2016, 35, 943. c) For the related
application of formate as a TH agent, see: V. H. Mai, S. H. Lee, G. I.
Nikonov, Chem. Select 2017, 2, 7751– 7757.
a) S. Werkmeister, C. Bornschein, K. Junge, M. Beller, Chem. Eur. J.,
2013, 19, 4437-4440; b) S. Werkmeister, C. Bornschein, K. Junge, M.
Beller, Eur. J. Org. Chem., 2013, 2013, 3671; c) For the use of
ammonium formate over Pd/C, see: M. Vilches-Herrera, S.
Werkmeister, K. Junge, A. Borner, M. Beller, Catal. Sci. Tech., 2014, 4,
629-632.
[15] I. D. Alshakova, I. Korobkov, L. G. Kuzmina, G. I. Nikonov, J.
Organomet. Chem. 2017, 853, 68-73.
[16] R.L. Chowdhury, J. E. Bäckvall, Chem. Commun. 1991, 1063-1064.
[17] J. E. Bäckvall, J. Organomet. Chem., 2002, 652, 105-111.
[18] Transfer hydrogenation is an equilibrium process and therefore 100%
conversion is thermodynamically not attainable.
[19] L. Q. Lu, Y. H. Li, K. Junge, M. Beller, Angew Chem Int. Edit. 2013, 52,
[3]
[4]
8382-8386.
[20] M. Crespo-Quesada, F. Cardenas-Lizana, A.-L. Dessimoz, L. Kiwi-
Minsker, ACS Catal. 2012, 2, 1773−1786.
[21] For examples of hydrogenation, see: a) D. Srimani, Y. Diskin-Posner,
Y. Ben-David, D. Milstein, Angew. Chem. Int. Ed. 2013, 52, 14131 –
14134; b) K. Semba, R. Kameyama, Y. Nakao, Synlett 2015, 26, 318–
322; c) F. Pape, N. O. Thiel, J. F. Teichert, Chem. Eur. J. 2015, 21,
15934 – 15938; d) M. Leutzsch, M. L. Wolf, P. Gupta, M. Fuchs,
W.Thiel, Farès, C.; Fürstner, A. Angew. Chem., Int. Ed. 2015, 54,
12431−12436; e) M. K. Karunananda, N. P. Mankad, J. Am. Chem.
Soc. 2015, 137, 14598−14601; f) T. Wakamatsu, K. Nagao, H. Ohmiya,
M. Sawamura, Organometallics 2016, 1354−1357; g) K. Tokmic, A. R.
Fout, J. Am. Chem. Soc. 2016, 13700−13705.
[5]
[6]
B. Paul, K. Chakrabarti, S. Kundu, Dalton. Trans. 2016, 45, 11162-
11171.
[22] For catalytic hydrogenation using Zn/water pair as reductant, see: T.
Schabel, C. Belger, B. Plietker, Org. Lett. 2013, 15, 2858-2861.
[23] For hydrogenation with the hydrosilane/water pair, see: a) K. Semba, T.
Fujihara, T. Xu, J. Terao, Y. Tsuji, Adv. Synth. Catal. 2012, 354, 1542–
1550; b) A. M. Whittaker, G. Lalic, Org. Lett. 2013, 15, 1112–1115; c)
N. Cox, H. Dang, A. M. Whittaker, G. Lalic, Tetrahedron 2014, 70, 4219
– 4231.
[24] For selected examples of transfer hydrogenation, see: a) G. Wienhöfer,
F. A. Westerhaus, R. V. Jagadeesh, K. Junge, H. Junge, M. Beller,
Chem. Commun., 2012, 48, 4827–4829; b) C. Belger, N. M. Neisius, B.
Plietker, Chem. Eur. J. 2010, 16, 12214 – 12220; c) I. N. Michaelides,
D. J. Dixon, Angew. Chem. Int. Ed. 2013, 52, 806 – 808.
[25] H. Meerwein, R. Schmidt, Justus Liebigs Ann. Chem. 1925, 444, 221-
238.
[7]
[8]
D. Kim, B. Kang, S. H. Hong, Org. Chem. Front. 2016, 3, 475-479.
a) D.-W. Wang, W. Zeng, Y-G. Zhou, Tetrahedron Asymm. 2007, 18,
1103-1107; b) M. Rueping, A. P. Antonchick, Angew. Chem. Int. Ed. ,
2007, 46, 4562-4565; c) Q.-S. Guo, D.-M. Du, J. Xu, Angew. Chem. Int.
Ed. , 2008, 47, 759-762; d) M. Rueping, F. Tato, F. R. Schoepke,
Chem. Eur. J. 2010, 16, 2688-2691; e) X.-F. Tu, L.-Z. Gong, Angew.
Chem. Int. Ed. , 2012, 51, 11346-11349.
a) C. Wang, C. Li, X. Wu, A. Pettman, J. Xiao, Angew. Chem. Int. Ed. ,
2009, 48, 6524-6528; b) V. Parekh, J. A. Ramsden, M. Wills,
Tetrahedron: Asymmetry, 2010, 21, 1549-1556; c) J. Tan, W. Tang, Y.
Sun, Z. Jiang, F. Chen, L. Xu, Q. Fan, J. Xiao, Tetrahedron, 2011, 67,
6206-6213; d) J. Wu, W. Tang, A. Pettman, J. Xiao, Adv. Synth. Catal. ,
2013, 357, 35-40; e) D. Talwar, H. Y. Li, E. Durham and J. Xiao, Chem.
Eur. J., 2015, 21, 5370-5379; f) L. Tao, Q. Zhang, S.-S. Li, X. Liu, Y.-M.
Liu and Y. Cao, Adv. Synth. Catal. , 2015, 357, 753-760; g) C. Xu, L.
Zhang, C. Dong, J. Xu, Y. Pan, Y. Li, H. Zhang, H. Li, Z. Yu, L. Xu, Adv.
Synth. Catal., 2016, 358, 567-572.
[9]
[26] Verley reported the TH of butyraldehyde the same year but used
gernaniol as reductant: A. Verley, Bull. Soc. Chim. Fr. 1925, 37, 871-
874.
[27] C.F. de Graauw, J. A. Peters, H. Van Bekkum, J. Huskens,
SYNTHESIS 1994, 1007-1017.
[10] Y. Maenaka, T. Suenobu, S. Fukuzumi, J. Am. Chem. Soc. 2012, 134,
[28] For recent applications of ethanol as a TH reagent, see: a) T. Zweifel,
J.-V. Naubron, T. Büttner, T. Ott, H. Grützmacher, Angew. Chem., Int.
Ed. 2008, 47, 3245-3249; b) T. Zweifel, D. Scheschkewitz, T. Ott, M.
Vogt, H. Grützmacher, Eur. J. Inorg. Chem. 2009, 5561- 5576; c) H.
Lundberg, H. Adolfson, Tetrahedron Lett. 2011, 52, 2754-2758; d) W.
P. Liu, M. L. Yuan, X. H. Yang, K. Li, J. H. Xie, Q. Zhou, Chem.
Commun., 2015, 51, 6123–6125; e) N. Castellanos-Blanco, A. Arévalo,
J. J. García, Dalton Trans., 2016, 45, 13604-13614.
[29] T.Seki, T. Nakajo, M. Onaka, Chem. Lett.2006, 35, 824-829.
[30] For recent examples of hydrodefluorination under the TH conditions,
see: a) V. H. Mai, G. I. Nikonov, ACS Catalysis, 2016, 6, 7956−7961; b)
S. Sabater, J. A. Mata, E. Peris, Organometallics 2015, 34, 1186; c) S.
Sabater, J. A. Mata, E. Peris, Nat. Commun. 2013, 4, 2553.
[31] J. S. M. Samec, J. E. Bäckvall, P. G. Andersson, P. Brandt, Chem. Soc.
Rev. 2006, 35, 237-248.
9417-9427.
[11] A. Dubey, E. Khaskin, ACS Catal. 2016, 6, 3998−4002.
[12] a) T. Jozak, D. Zabel, A. Schubert, Y. Sun, W. R. Thiel, Eur. J. Inorg.
Chem. 2010, 5135-5145; b) L. T. Ghoochany, S. Farsadpour, Y. Sun,
W .R. Thiel, Eur. J. Inorg. Chem. 2011, 3431-3437.
[13] a) H. Deng, Z. Yu, J. Dong, S. Wu, Organometallics 2005, 24, 4110-
4112; b) W.J. Ye, M. Zhao, Z.K. Yu, Chem.-Eur. J. 2012, 18, 10843-
10846; c) W.W. Jin, L.D. Wang, Z.K. Yu, Organometallics 2012, 31,
5664-5667; d) W.M. Du, P. Wu, Q.F. Wang, Z.K. Yu, Organometallics
2013, 32, 3083-3090; e) W. Du, Q. Wang, L. Wang, Z. Yu,
Organometallics 2014, 33, 974-982.
[14] a) D. B. Grotjahn, S. Van, D. Combs, D. A. Lev, C. Schneider, C.D.
Incarvito, K.-C. Lam, G. Rossi, A.L. Rheingold, M. Rideout, C. Meyer,
G. Hernandez, L. Mejorado, Inorg. Chem. 2003, 42, 3347-3355; b) D.
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