4
Tetrahedron Letters
Supplementary Data
Supplementary data associated with this article can be found,
in the online version, at
References and notes
1
.
(a) Kishner, N. J. Russ. Phys. Chem. Soc. 1911, 43, 582. (b)
Wolff, L. Justus Liebigs Ann. Chem. 1912, 394, 86.
2
3
.
.
Huang-Minlon, J. Am. Chem. Soc. 1946, 68, 2487.
(a) Kuethe, J. T.; Childers, K. G.; Peng, Z.; Journet, M.;
Humphrey, G. R.; Vickery, T.; Bachert, D.; Lam, T. T. Org.
Process Res. Dev. 2009, 13, 576. (b) Yamabe, S.; Zeng, G.; Guan,
W.; Sakaki, S. Beilstein J. Org. Chem. 2014, 10, 259
4
5
.
.
(a) Huang, J.-L.; Dai, X.-J.; Li, C.-J. Eur. J. Org. Chem. 2013,
6
(
4
496. (b) Dai, X.-J.; Li, C.-J. J. Am. Chem. Soc. 2016, 138, 5433.
c) Bauer, J. O.; Chakraborty, S.; Milstein, D. ACS Catal. 2017, 7,
462.
Figure 1. Proposed mechanism
(a) Cárdenas, D. J. Angew. Chem. Int. Ed. 2003, 42, 384. (e)
Kacprzynski, M. A.; Hoveyda, A. H. J. Am. Chem. Soc. 2004,
To test the effect of Pd/C catalyzed reduction of carbonyls
under scale-up conditions, benzophenone 1a (10.0 g) was input
into the reaction under standard conditions A and 9.1 g 2a was
attained with 98.9% yield (Table 3, Entry 1). And the recycle
time of Pd/C catalyst was also tested. Pleasingly, the catalytic
activity of Pd/C catalyst was decreased slightly at second and
third utility (entries 2 and 3, both yields 96.7%). The results
indicated that the recyclable Pd/C catalyst may be appropriate for
the scale-up practice.
1
26, 10676. (c) Millet, R.; Bernardez, T.; Palais, L.; Alexakis, A.
Tetrahedron Lett. 2009, 50, 3474. (d) Fañanás-Mastral, M.; Pérez,
M.; Bos, P. H.; Rudolph, A.; Harutyunyan, S. R.; Feringa, B. L.
Angew. Chem. Int. Ed. 2012, 51, 1922. (e)You, H. Z.; Rideau, E.;
Sidera, M.; Fletcher, S. P. Nature 2015, 517, 351. (f) Zhu, D.; Lv,
L.; Qiu, Z.; Li, C.-J. J. Org. Chem. 2019, 84, 6312. (g) Zhu, C.;
Zhang, J. Chem. Commun. 2019, 55, 2793. (h) Li, C.-J.; Huang, J.;
Dai, X.-J.; Wang, H.; Chen, N.; Wei, W.; Zeng, H.; Tang, J.; Li,
C.; Zhu, D.; Lv, L. Synlett 2019, 30, 1508.
6
7
.
.
Dai, X.-J.; Wang, H.; Li, C.-J. Angew. Chem. Int. Ed. 2017, 56,
6
302.
Table 3. Test of scale-up conditions and recycling of Pd/C
(a) Chen, N.; Dai, X.-J.; Wang, H.; Li, C.-J. Angew. Chem. Int.
Ed. 2017, 56, 6260. (b) Yan, S.-S.; Zhu, L.; Ye, J.-H.; Zhang, Z.;
Huang, H.; Zeng, H.; Li, C.-J.; Lan, Y.; Yu, D.-G. Chem. Sci.
catalysta
2
018, 9, 4873.
8
.
Osdene, T. S.; Timmis, G. M.; Maguire, M. H.; Shaw, G.;
Goldwhite, H.; Saunders, B. C.; Clark, E. R.; Epstein, P. F.;
Lamchen, M.; Stephen, A. M.; Tipper, C. F. H.; Eaborn, C.;
Mukerjee, S. K.; Seshadri, T. R.; Willenz, J.; Robinson, R.;
Thomas, A. F.; Hickman, J. R.; Kenyon, J.; Crocker, H. P.; Hall,
R. H.; Burnell, R. H.; Taylor, W. I.; Watkins, W. M.; Barton, D.
H. R.; Ives, D. A. J.; Thomas, B. R. J. Chem. Soc. 1955, 2038.
Cram, D. J.; Sahyun, M. R. V. J. Am. Chem. Soc. 1962, 84, 1734.
b
Recyclable Times
m (Pd/C)
m (1a)
10.0 g
10.0 g
10.0 g
m (2a)
9.1 g
8.9 g
8.9 g
Yield (%)
st
1
1.1 g
98.9
9
.
nd
c
10. Grundon, M. F.; Henbest, H. B.; Scott, M. D. J. Chem. Soc. 1963,
855.
11. Caglioti, L.; Magi, M. Tetrahedron 1963, 19, 1127.
2
/
96.7
1
rd
c
3
/
96.7
1
1
2. Crestini, C.; Saladino, R. Synth. Commun. 1994, 24, 2835.
3. Eisenbraun, E. J.; Payne, K. W.; Bymaster, J. S. Ind. Eng. Chem.
Res. 2000, 39, 1119.
4. Furrow, M. E.; Myers, A. G. J. Am. Chem. Soc. 2004, 126, 5436.
5. Agee, B. M.; Mullins, G.; Biernacki, J. J.; Swartling, D. J. Green
Chem. Lett. Rev. 2014, 7, 383.
a
1
2 4 2 2
a (10.0 g), N H ·H O (11.0 g, 4.0 equiv), Pd/C, H O (9.9 g, 10.0 equiv),
b c
EtOH (50.0 mL), 100 °C, 24 h. Isolated yield. Pd/C was added after washed
with water (10 mL) and EtOH (5 mL) respectively after filtered from the
previous reaction system.
1
1
1
1
1
6. Newman, S. G.; Gu, L.; Lesniak, C.; Victor, G.; Meschke, F.
Green Chem. 2014, 16, 176.
7. Cranwell, P. B.; Russell, A. T.; Smith, C. D. Synlett 2016, 27,
In summary, we have developed an effective reduction of
ketones and aldehydes with Pd/C as catalyst. Hydrazine hydrate,
hydrogen gas or ammonium formate can be applied as reductant
independently. The simple conditions can be carried out in
normal solvent without extra strong base and the good to
excellent yields were obtained. The reaction can be scaled-up to
1
31.
8. Rahaim Jr., R. J.; Maleczka Jr., R. E. Org. Lett. 2011, 13, 584.
19. Kalutharage, N.; Yi, C. S. J. Am. Chem. Soc. 2015, 137, 11105.
20. Chen, X.; Zhou, X-Y.; Wu, H.; Lei, Y.-Z.; Li, J.-H. Synth.
Commun. 2018, 48, 2475.
2
1. (a) Chen, Z.; Zeng, H.; Girard, S. A.; Wang, F.; Chen, N.; Li, C.-J.
Angew. Chem. Int. Ed. 2015, 54, 14487. (b) Qiu, Z.; Li, J.-S.; Li,
C.-J. Chem. Sci. 2017, 8, 6954. (c) Li, J.-S.; Qiu, Z.; Li, C.-J. Adv.
Synth. Catal. 2017, 359, 3648. (d) Cao, D.; Zeng, H.; Li, C.-J.
ACS Catal. 2018, 8, 8873. (e) Zeng, H.; Wang, Z.; Li, C.-J. Angew.
Chem. Int. Ed. 2019, 58, 2859. (f) Wang, Z.; Zeng, H.; Li, C.-J.
Org. Lett. 2019, 21, 2302. (g) Qiu, Z.; Lv, L.; Li, J.; Li, C.-C.; Li,
C.-J. Chem. Sci. 2019, 10, 4775. (h) Dominguez-Huerta, A.;
Perepichka, I.; Li, C.-J. ChemSusChem 2019, 12, 2999.
1
0 grams with excellent yield and the heterogeneous Pd/C can be
recovered and recycled with times. Furthermore, the
3
mechanism has been proposed and verified preliminarily
according to the controlled experiments.
Acknowledgments
The work was supported by the Natural Science Foundation of
Guizhou Province (Grant No. qiankehejichu [2018] number
1
141), the Science and Technology Foundation Project of
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Liupanshui (Grant No. 52020-2018-04-10) and the Youth
Science and Technology Talent Development Project in
Education Department of Guizhou Province (Grant
No.qianjiaohe KY zi [2017] number 261).