ACS Catalysis
Page 8 of 10
For a recent example of organo-catalytic promoted hydrosilyla-
tion of amides to amines see: (i) Blondiaux, E.; Cantat T. Chem.
Commun. 2014, 50, 9349-9352.
with three cycles of vacuum/argon and argon atmosphere
was established. Then, dry isopropanol (1 ml) and the cor-
responding amount of KOtBu (1-10 mol%) previously dis-
solved in dry isopropanol (1 ml) were sequentially added
under argon and the vials were then placed into a 300 mL
autoclave. Once sealed, the autoclave was purged three
times with 30 bar of hydrogen, then pressurized to the
desired hydrogen pressure (15, 30 or 50 bar) and placed
into an aluminium block which was preheated to the de-
sired temperature (80-150 °C). After the corresponding
reaction time 3-18 h, the autoclave was cooled in an ice
bath and the remaining gas was carefully released. Finally,
n-hexadecane (50 mg) was added as an external standard,
the reaction mixture was diluted with ethyl acetate and
analysed by GC.
1
2
3
4
5
6
7
8
(5)(a) Hirosawa, C.; Wakasa, N.; Fuchikami, T. Tetrahedron Lett.,
1996, 37, 6749-6752. (b) Beamson, G.; Papworth, A. J.; Philipps,
C.; Smith, A. M.; Whyman, R. J. Catal., 2010, 269, 93-102. (c)
Beamson, G.; Papworth, A. J.; Philipps, C.; Smith, A. M.; Why-
man, R. J. Catal., 2011, 278, 228-238. (d) Stein, M.; Breit, B. An-
gew. Chem. Int. Ed. 2013, 52, 2231-2234. (e) Burch, R.; Paun, C.;
Cao, X.-M.; Crawford, P.; Goodrich, P.; Hardacre, C.; Hu, P.;
McLaughlin, L.; Sá, J.; Thompson, J. M. J. Catal., 2011, 283, 89-97.
(f) Coetzee, J.; Manyar, H. G.; Hardacre, C.; Cole-Hamilton, D. J.
ChemCatChem 2013, 5, 2843-2847.
(6) (a) Núñez Magro, A. A.; Eastham, G. R.; Cole-Hamilton, D. J.
Chem. Commun. 2007, 3154-3156. (b) Dodds, D. L.; Coetzee, J.;
Klankermayer, J.; Brosinski, S.; Leitner, W.; Cole-Hamilton, D. J.
Chem. Commun. 2012, 48, 12249-12262. (c) Coetzee, J.; Dodds, D.
L.; Klankermayer, J.; Brosinsky, S.; Leitner W.; Slawin, A. M. Z.;
Cole-Hamilton, D. J. Chem. Eur. J., 2013, 19, 11039-11050. (d) vom
Stein, T.; Meuresch, M.; Limper, D.; Schmitz, M.; Hölscher, M.;
Coetzee, J.; Cole-Hamilton, D. J.; Klankermayer, J.; Leitner W. J.
Am. Chem. Soc. 2014, 136, 13217-13225.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ASSOCIATED CONTENT
Supporting Information. General information concerning
synthesis and hydrogenation reactions, NMR and IR spectra
of 1, 2 and 3, crystal data of syn-2. This material is available
(7) (a) Noyori, R.; Yamakawa, M.; Hashiguchi, S. J. Org. Chem.
2002, 66, 7931-7944. (b) Gunanathan, C.; Milstein, D. Acc. Chem.
Res. 2011, 44, 588–602. (c) Schneider, S.; Meiners, J.; Askevold, B.
Eur. J. Inorg. Chem. 2012, 412–429.
AUTHOR INFORMATION
Corresponding Author
(8) Cantillo, D. Eur. J. Inorg. Chem, 2011, 3008-3013.
(9) (a) Balaraman, E.; Gnanaprakasam, B.; Shimon, L. J. W.;
Milstein, D. J. Am. Chem. Soc. 2010, 132, 16756-16758. (b) John, J.
M.; Bergens, S. H. Ang. Chem. Int. Ed., 2011, 50, 10377-10380. (c)
Ito, M.; Ootsuka, T.; Watari, R.; Shiibashi, A.; Himizu, A.; Ikari-
ya, T. J. Am. Chem. Soc. 2011, 133, 4240-4242. (d) Miura, T.; Held,
I. E.; Oishi, S.; Naruto, M.; Saito, S. Tetrahedron Lett., 2013, 54,
2674-2678. (e) Barrios-Francisco, R.; Balaraman, E.; Diskin-
Posner, Y.; Leitus, G.; Shimon, L. J. W.; Milstein, D. Organome-
tallics 2013, 32, 2973-2982. (f) John, J. M.; Takebayashi, S.; Dabral,
N.; Miskolzie, M.; Bergens, S. H. J. Am. Chem. Soc. 2013, 135,
8578-8584. (g) Kita, Y.; Higuchi, T.; Mashima, K. Chem. Com-
mun., 2014, 50, 11211-11213. (h) John, J. M.; Loorthuraja, R.; Anto-
niuk, E.; Bergens, S. H. Catal. Sci. Technol., 2015, 5, 1181-1186.
(10) a) Gunanathan, C.; Milstein, D. Chem. Rev. 2014, 114, 12024-
12087; b) Younus, H. A.; Su, W.; Ahmad, N.; Chen, S.; Verpoort,
F. Adv. Synth. Catal. 2015, 357, 283-330.
(11) Representative applications: a) Zhang, J.; Leitus, G.; Ben-
David, Y.; Milstein, D. Angew. Chem., Int. Ed. 2006, 45, 1113-1115.
b) Spasyuk, D.; Smith, S.; Gusev, D. G. Angew. Chem. Int. Ed.
2012, 51, 2772-2775. c) Fogler, E.; Garg, J. A.; Hu, P.; Leitus, G.;
Shimon, L. J. W.; Milstein D. Chem. Eur. J. 2014, 20, 15727-15731.
d) Spasyuk, D.; Vicent, C.; Gusev, D. G. J. Am. Chem. Soc. 2015,
137, 3743-3746. e) Fuentes, J. A.; Smith, S. M.; Scharbert, M. T.;
Carpenter, I.; Cordes, D. B.; Slawin, A. M. Z.; Clarke M. L. Chem.
Eur. J. 2015, 21, 10851 – 10860. References to further transfor-
mations catalyzed by PNN-Ru complexes are to be found in reff.
10.
Author Contributions
‡These authors contributed equally.
Funding Sources
The authors would like to thank the ACS Pharmaceutical
Roundtable for financial support and its members, especially
Dr. Fabrice Gallou, for fruitful scientific discussions. In addi-
tion, support by the state of Mecklenburg-Vorpommern and
the BMBF are acknowledged. J.R.C.-A. thanks the Ramon
Areces Foundation for a postdoctoral fellowship.
REFERENCES
(1) (a) Eller, K.; Henkes, E.; Rossbacher, R.; Hoke; H. Ullman’s
Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim,
2000, Amines, Aliphatic. DOI: 10.1002/14356007.a02_001 (b)
Amines: Synthesis, Properties and Applications; Lawerence, S. A.,
Ed.; Cambridge University: Cambridge, 2006.
(2) (a) Dodds, D.; Cole-Hamilton, D. J. in Sustainable Catalysis:
Challenges and Practices for the Pharmaceutical and Fine Chemi-
cal Industries; Dunn, P. J.; Hii, K. K.; Krische, M. J.; Williams M.
T., Eds.; John Wiley and Sons, Inc.: Hoboken, New Jersey, 2013;
pp. 1-36. (b) Smith, A. M.; Whyman, R. Chem. Rev. 2014, 114,
5477-5510.
(3) Lampland, N. L.; Hovey, M.; Mukherjee, D.; Sadow, A. D.
ACS Catal. 2015, 5, 4219−4226.
(12) a) Junge, K.; Wendt, B.; Westerhaus, F. A.; Spannenberg, A.;
Jiao, H.; Beller, M. Chem. Eur. J. 2012, 18, 9011-9018. b)
Werkmeister, S.; Junge, K.; Wendt, B.; Spannenberg, A.; Jiao, H.;
Bornschein, C.; Beller, M. Chem. Eur. J. 2014, 20, 4227-4231.
(13) Heterocyclic chemistry, 5th ed Joule, J. A.; Mills. K.; John
Wiley and Sons, Inc.: Chichester, United Kingdom, 2010.
(14) The related pincer imine ligand derived from the condensa-
(4) Selected recent examples (a) Zhou, S.; Junge, K.; Addis, D.;
Das, S.; Beller, M. Angew. Chem. Int. Ed. 2009, 48, 9507-9510. (b)
Das, S.; Addis, D.; Zhou, S.; Junge, K.; Beller, M. J. Am. Chem.
Soc. 2010, 132, 1770-1771. (c) Das, S.; Addis, D.; Junge, K.; Beller,
M. Chem. Eur. J. 2011, 17, 12186-12192. (d) Das, S.; Wendt, B.;
Mçller, K.; Junge, K.; Beller, M. Angew. Chem. Int. Ed. 2012, 51,
1662–1666. (e) Park, S.; Brookhart, M. J. Am. Chem. Soc. 2012, 134,
640–653. (f) Cheng, C.; Brookhart, M. J. Am. Chem. Soc. 2012, 134,
11304–11307. (g) Reeves, J. T.; Tan, Z.; Marsini, M. A.; Han, Z. S.;
Xu, Y.; Reeves, D. C.; Lee, H.; Lu, B. Z.; Senanayakea, C. H. Adv.
Synth. Catal. 2013, 355, 47 – 52. (h) Dombray, T.; Helleu, C.;
Darcel, C.; Sortaisa, J.-B. Adv. Synth. Catal. 2013, 355, 3358 – 3362.
tion
of
1-methyl-2-imidazolecarboxaldehyde
and
2-
(diphenylphosphino)ethylamine and its Ni(II) complex have
been reported. The latter has been applied as catalyst in the oli-
gomerization of ethylene: Boudier, A.; Breuil, P.-A. R.; Magna, L.;
Olivier-Bourbigou, H.; Braunstein, P. J. Organomet Chem., 2012,
718, 31-37.
ACS Paragon Plus Environment