Citation: Sun Guofeng, He Yunqing, Tian Chong, Borzov Maxim, Hu Qishan, Nie Wanli. B(C₆F₅)₃-Catalyzed Chemoselective Reduction of Carbonyl Compounds under Water Conditions[J]. Acta Chimica Sinica, ;2019, 77(2): 166-171. doi: 10.6023/A18100423 shu

B(C₆F₅)₃-Catalyzed Chemoselective Reduction of Carbonyl Compounds under Water Conditions

a.
Sichuan Province Key Laboratory of Natural Products and Small Molecule Synthesis, Chemical Department of Leshan Normal University, Leshan 614000, China
b.
College of Chemistry and Chemical Engineering, Sichuan University of Arts and Science, Dazhou 635000, China

Corresponding author: Nie Wanli, niewl126@126.com
Received Date: 11 October 2018
Available Online: 7 February 2018
Fund Project: Scientific Research Fund of Leshan Normal University Z1308Project supported by the National Natural Science Foundation of China (No. 21542011), and Scientific Research Fund of Leshan Normal University (Z1414, Z1308)the National Natural Science Foundation of China 21542011Scientific Research Fund of Leshan Normal University Z1414

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Recently, the research work concerning B(C₆F₅)₃ catalyzed reduction of carbonyl compounds revealed that this Lewis acid B(C₆F₅)₃ presents, actually, a rather water-tolerant system. This fact considerably broadens the scope of the water/base tolerant frustrated Lewis pairs (FLP) chemistry. In this research, an efficient chemoselective reduction of aldehydes and ketones to alcohols catalyzed by the Lewis acid B(C₆F₅)₃ has been developed. It is the first report about the chemoselective reduction of carbonyl compounds under aqueous conditions catalyzed by FLPs with hydridosilanes as reducing agents. The selectivity and activity of different hydridosilanes and the influence of substituents in carbonyl compounds have been studied. The effect of water concentration on the chemoselectivity of the reaction has also been investigated. It has been found that a 2~3 fold excess of water relatively to hydridosilanes usually exhibits better selectivity and overall yields than in the equimolar case. The reduction reaction can even be successfully performed with pure water as a solvent without any loss of the reactivity. Such a procedure has been successfully applied to reduce 14 differently substituted aldehydes and ketones into alcohols with up to 100% yields under mild conditions, but failed in case of the diaryl substituted ketones. Both experimental and computational methods have been performed to confirm the possibility of the water mediated mechanism and the effects of different Lewis bases on the LB——H-OH——LA three-component aggregates. These mechanistic studies have revealed that such water mediation between a carbonyl compound and a catalyst advantageously (i) activates the C=O group by protonation and (ii) fixes the catalytic borane moiety by formation of a B-O bond, which to some extent prevents the direct hydrolysis of hydridosilane and makes the reaction possible under moist conditions. Detailed clarification of the actual role of water in the reduction reaction of question will promote the further development of FLP-catalyzed and related reactions in the "green" chemistry field.
- frustrated Lewis pairs,
- chemoselective reduction,
- carbonyl compound,
- water condition,
- water mediated interaction
1. [1]
  de Vries, J. G.; Elsevier, C. J. The Handbook of Homogeneous Hydrogenation, Wiley-VCH, Weinheim, Germany, 2008.
2. [2]
  Sorella, G. L.; Sperni, L.; Canton, P.; Coletti, L.; Fabris, F.; Strukul, G.; Scarso, A. J. Org. Chem. 2018, 83(14), 7438. doi: 10.1021/acs.joc.8b00314
3. [3]
  Leischner, T.; Spannenberg, A.; Junge, K.; Beller, M. Organometallics 2018, DOI:10.1021/acs.organomet.8b00410. doi: 10.1021/acs.organomet.8b00410
4. [4]
  Cao, Y.; Ma, R.; Wang, N.; Wang, M.-Y.; Li, X.-D.; He, L.-N. J. CO₂ Util. 2018, 24, 328. doi: 10.1016/j.jcou.2018.01.019
5. [5]
  Call, A.; Lloret-Fillol, J. Chem. Commun. 2018, 54, 9643. doi: 10.1039/C8CC04239J
6. [6]
  Zhang, J.; Qu, L.; Shi, G.; Liu, J.; Chen, J.; Dai, L. Angew. Chem., Int. Ed. 2016, 55, 2230. doi: 10.1002/anie.201510495
7. [7]
  Chakraborty, S.; Bhattacharya, P.; Dai, H.; Guan, H. Acc. Chem. Res. 2015, 48, 1995. doi: 10.1021/acs.accounts.5b00055
8. [8]
  Guo, J.; Chen, J.; Lu, Z. Chem. Commun. 2015, 51, 5725. doi: 10.1039/C5CC01084E
9. [9]
  Dai, L.; Xue, Y.; Qu, L.; Choi, H. J.; Baek, J. B. Chem. Rev. 2015, 115, 4823. doi: 10.1021/cr5003563
10. [10]
  Mahdi, T.; Stephan, D. W. Angew. Chem., Int. Ed. 2015, 54, 8511. doi: 10.1002/anie.201503087
11. [11]
  Volkov, A.; Gustafson, K. P. J.; Tai, C. W.; Verho, O.; Baeckvall, J. E.; Adolfsson, H. Angew. Chem., Int. Ed. 2015, 54, 5122. doi: 10.1002/anie.v54.17
12. [12]
  Parks, D. J.; Piers, W. E. J. Am. Chem. Soc. 1996, 118, 9440. doi: 10.1021/ja961536g
13. [13]
  Stephan, D. W.; Erker, G. Angew. Chem., Int. Ed. 2010, 49, 46. doi: 10.1002/anie.200903708
14. [14]
  Liu, Y.-B.; Du, H.-F. Acta Chim. Sinica 2014, 72, 771(in Chinese).
15. [15]
  Xuan, Q.; Zhao, C.; Song, Q. Org. Biomol. Chem. 2017, 15, 5140. doi: 10.1039/C7OB00820A
16. [16]
  Wei, S.; Du, H. J. Am. Chem. Soc. 2014, 136, 12261. doi: 10.1021/ja507536n
17. [17]
  Oestreich, M.; Hermeke, J.; Mohr, J. Chem. Soc. Rev. 2015, 44, 2202. doi: 10.1039/C4CS00451E
18. [18]
  Stephan, D. W.; Erker, G. Angew. Chem., Int. Ed. 2015, 54, 6400. doi: 10.1002/anie.201409800
19. [19]
  Ren, X.; Du, H. J. Am. Chem. Soc. 2016, 38, 810.
20. [20]
  Stephan, D. W.; Greenberg, S.; Graham, T. W.; Chase, P.; Hastie, J. J.; Geier, S. J.; Farrell, J. M.; Brown, C. C.; Heiden, Z. M.; Welch, G. C.; Ullrich, M. Inorg. Chem. 2011, 50, 12338. doi: 10.1021/ic200663v
21. [21]
  Mahdi, T. Stephan, D. W. J. Am. Chem. Soc. 2014, 136, 15809. doi: 10.1021/ja508829x
22. [22]
  Scott, D. J.; Fuchter, M. J.; Ashley, A. E. J. Am. Chem. Soc. 2014, 136, 15813. doi: 10.1021/ja5088979
23. [23]
  Scott, D. J.; Simmons, T. R.; Lawrence, E. J.; Wildgoose, G. G.; Fuchter, M. J.; Ashley, A. E. ACS Catal. 2015, 5, 5540. doi: 10.1021/acscatal.5b01417
24. [24]
  Gyömöre, A.; Bakos, M.; Földes, T.; Papai, I.; Domja, N. A.; Soós, T. ACS Catal. 2015, 5, 5366. doi: 10.1021/acscatal.5b01299
25. [25]
  Parks, D. J.; Blackwell, J. M.; Piers, W. E. J. Org. Chem. 2000, 65, 3090. doi: 10.1021/jo991828a
26. [26]
  Piers, W. E.; Marwitz, A. J. V.; Mercier, L. G. Inorg. Chem. 2011, 50, 12252. doi: 10.1021/ic2006474
27. [27]
  Nie, W.-L.; Klare, H. F. T.; Oestreich, M.; Froehlich, R.; Kehr, G.; Erker, G. Z. Naturforsch. 2012, 67b, 987.
28. [28]
  Ermeke, J.; Mewald, M.; Oestreich, M. J. Am. Chem. Soc. 2013, 135, 17537. doi: 10.1021/ja409344w
29. [29]
  Houghton, A. Y.; Hurmalainen, J.; Mansikkamaeki, A.; Piers, W. E.; Tuononen, H. M. Nat. Chem. 2014, 6, 983. doi: 10.1038/nchem.2063
30. [30]
  Nimmagadda, R. D.; McRae, C. Tetrahedron Lett. 2006, 47, 5755. doi: 10.1016/j.tetlet.2006.06.007
31. [31]
  Chatterjee, I.; Porwal, D.; Oestreich, M. Angew. Chem., Int. Ed. 2017, 56, 3389. doi: 10.1002/anie.201611813
32. [32]
  Yang, W.-Y.; Gao, L.; Lu, J.; Song, Z.-L. Chem. Commun. 2018, 54, 4834. doi: 10.1039/C8CC01163J
33. [33]
  Parks, D. J.; Piers, W. E. J. Am. Chem. Soc. 1996, 118, 9440. doi: 10.1021/ja961536g
34. [34]
  Blackwell, J. M.; Foster, K. L.; Beck, V. H.; Piers, W. E. J. Org. Chem. 1999, 64, 4887. doi: 10.1021/jo9903003
35. [35]
  Tahara, A.; Sunada, Y.; Takeshita, T.; Inoue, R.; Nagashima, H. Chem. Commun. 2018, 54, 11192. doi: 10.1039/C8CC04780D
36. [36]
  Hu, X.; Tian, C.; Borzov, M.; Nie, W.-L. Acta Chim. Sinica, 2015, 73, 1025(in Chinese).
37. [37]
  Tian, C.; Jiang, Y.; Borzov, M.; Nie, W.-L. Acta Chim. Sinica 2015, 73, 1203(in Chinese).
38. [38]
  Wen, Z.-G.; Tian, C.; Borzov, M.; Nie, W.-L. Acta Chim. Sinica 2016, 74, 498(in Chinese).
39. [39]
  Nie, W.-L.; Sun, G.-F.; Tian, C.; Borzov, M. Z. Naturforsch. 2016, 71(10)b, 1029.
40. [40]
  Zhang, L.-W.; Wen, Z.-G.; Borzov, M.; Nie, W.-L. Acta Chim. Sinica 2017, 75, 819(in Chinese).
41. [41]
  Fasano, V.; Radcliffe, J. E.; Ingleson, M. J. ACS Catal. 2016, 6(3), 1793. doi: 10.1021/acscatal.5b02896
42. [42]
  Fasano, V.; Ingleson, M. J. Chem. Eur. J. 2017, 23(9), 2217. doi: 10.1002/chem.201605466
43. [43]
  Sun, G.-F.; Su, M.; Fang, J.; Borzov, M.; Nie, W.-L. Acta Chim. Sinica 2017, 75, 824(in Chinese).
44. [44]
  He, Y.-Q.; Teng, J. W.; Tian, C.; Borzov, M.; Hu, Q. S.; Nie, W.-L. Acta Chim. Sinica 2018, 76, 774(in Chinese).
45. [45]
  He, Y.-Q.; Zou, M.-Y.; Xue, Y.; Hu, Q.-S.; Borzov, M. V.; Nie, W.-L. Mechanism Aspects of the B(C₆F₅)₃ Catalyzed Reductive Amination, Chem-Eur. J. 2018, Submitted.
46. [46]
  Bergamaschi, G.; Lascialfari, L.; Pizzi, A.; Espinoza, M. I. M.; Demitri, N.; Milani, A.; Gori, A.; Metrangolo, P. Chem. Commun. 2018, DOI:10.1039/C8CC06010. doi: 10.1039/C8CC06010
47. [47]
  Beck, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
48. [48]
  Parr, R. G.; Yang, W. Density Functional Theory of Atoms and Molecules, Oxford University Press, Oxford, 1989.
49. [49]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams-Young, D.; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O. Nakai, H. Vreven, T. Throssell, K. Montgomery, J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian 16, Revision A.03, Gaussian, Inc., Wallingford CT, 2016.
50. [50]
  The typical ¹¹B NMR signal of[R₃NH] [HO-B(C₆F₅)₃] is located at δ-3.9; the corresponding ¹⁹F NMR signals of o-, p-and m-F in[HO-B(C₆F₅)₃] are at δ -135.6, -160.1, -164.8, respectively.
51. [51]
  Bergquist, C.; Bridgewater, B. M.; Harlan, C. J.; Norton, J. R.; Friesner, R. A.; Parkin, G. J. Am. Chem. Soc. 2000, 122, 10581. doi: 10.1021/ja001915g
52. [52]
  Di Saverio, A.; Focante, F.; Camurati, I.; Resconi, L.; Beringhelli, T.; D'Alfonso, G.; Donghi, D.; Maggioni, D.; Mercandelli, P.; Sironi, A. Inorg. Chem. 2005, 44, 5030. doi: 10.1021/ic0502168
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B(C₆F₅)₃-Catalyzed Chemoselective Reduction of Carbonyl Compounds under Water Conditions