Efficient Ruthenium(II)-Catalyzed Direct Reductive Amination of Aldehydes under Mild Conditions Using Hydrosilane as the Reductant­

Bin Li; Jianxiong Zheng; Weifeng Zeng; Yibiao Li; Lu Chen

doi:10.1055/s-0036-1588092

Synthesis, Table of Contents

Synthesis 2017; 49(06): 1349-1355
DOI: 10.1055/s-0036-1588092

paper

Efficient Ruthenium(II)-Catalyzed Direct Reductive Amination of Aldehydes under Mild Conditions Using Hydrosilane as the Reductant

Authors

Bin Li*

School of Chemical & Environmental Engineering, Wuyi University, Jiangmen 529020, Guangdong Province, P. R. of China Email: binli@wyu.edu.cn Email: leeyib268@126.com
Jianxiong Zheng

School of Chemical & Environmental Engineering, Wuyi University, Jiangmen 529020, Guangdong Province, P. R. of China Email: binli@wyu.edu.cn Email: leeyib268@126.com
Weifeng Zeng

School of Chemical & Environmental Engineering, Wuyi University, Jiangmen 529020, Guangdong Province, P. R. of China Email: binli@wyu.edu.cn Email: leeyib268@126.com
Yibiao Li*

School of Chemical & Environmental Engineering, Wuyi University, Jiangmen 529020, Guangdong Province, P. R. of China Email: binli@wyu.edu.cn Email: leeyib268@126.com
Lu Chen

School of Chemical & Environmental Engineering, Wuyi University, Jiangmen 529020, Guangdong Province, P. R. of China Email: binli@wyu.edu.cn Email: leeyib268@126.com

Abstract

All articles of this category

Abstract

A direct reductive amination of aldehydes with anilines is performed with a ruthenium(II)-(arene) catalyst. The [RuCl₂(p-cymene)]₂/Ph₂SiH₂ catalytic system is very efficient for the synthesis of secondary amines and tertiary amines in good yields, and is highly chemoselective, tolerating a wide range of functional groups, such as NO₂, CN, CO₂Me, F, Cl, Br, OMe, Me, furyl and alkyl. We also report an interesting direductive amination of 2-ethylbutanal.

Key words

ruthenium catalysis - hydrosilane - reductive amination - amines - aldehydes

Full Text

References

References

For selected representative books, see:

1a Larock RC. Comprehensive Organic Transformations, A Guide to Functional Group Preparations. Wiley-VCH; New York: 1989
1b Ricci A. Modern Amination Methods . Wiley-VCH; New York: 2000
1c Lawrence SA. Amines: Synthesis, Properties and Applications . Cambridge University Press; Cambridge: 2004
1d Amino Group Chemistry. From Synthesis to the Life Sciences. Ricci A. Wiley-VCH; Weinheim: 2008

For reviews, see:

2a Spindler F, Blaser H.-U In Transition Metals for Organic Synthesis . 2nd ed., Vol. 2; Beller M, Bolm C. Wiley-VCH; Weinheim: 2004: 113
2b Blaser H.-U, Spindler F In The Handbook of Homogeneous Hydrogenation . Vol. 3. de Vries JG, Elsevier CJ. Wiley-VCH; Weinheim: 2007: 1193
2c Blaser H.-U, Malan C, Pugin B, Spinder F, Steiner H, Studer M. Adv. Synth. Catal. 2003; 345: 103
2d Tang W, Zhang X. Chem. Rev. 2003; 103: 3029
2e Nugent TC, El-Shazly M. Adv. Synth. Catal. 2010; 352: 753
2f Rueping M, Sugiono E, Schoepke FR. Synlett 2010; 852

3a Xie J.-H, Zhu S.-F, Zhou Q.-L. Chem. Rev. 2011; 111: 1713
3b Fleury-Brégeot N, de la Fuente V, Castillon S, Claver C. ChemCatChem 2010; 2: 1346
3c Transition Metals for Organic Synthesis . 2nd ed.; Beller M, Bolm C. Wiley-VCH; Weinheim: 2004
3d Fabrello A, Bachelier A, Urrutigoïty M, Kalck P. Coord. Chem. Rev. 2010; 254: 273

4a Gladiali S, Alberico E In Transition Metals for Organic Synthesis . Beller M, Bolm C. Wiley-VCH; Weinheim: 2004
4b Clapham SE, Hadzovic A, Morris RH. Coord. Chem. Rev. 2004; 248: 2201
4c Samec JS. M, Bäckvall J.-E. Chem. Eur. J. 2002; 8: 2955
4d Casey CP, Johnson JB. J. Org. Chem. 2003; 68: 1998
4e Zhu C, Saito K, Yamanaka M, Akiyama T. Acc. Chem. Res. 2015; 48: 388

5a Xiong B, Zhang S, Jiang H, Zhang M. Org. Lett. 2016; 18: 724
5b Xiong B, Li Y, Lv W, Tan Z, Jiang H, Zhang M. Org. Lett. 2015; 17: 4054
5c Xie F, Zhang M, Jiang H, Chen M, Lv W, Zheng A, Jian X. Green. Chem. 2015; 17: 279

6 Seyden-Penne J. Reductions by the Alumino- and Borohydrides in Organic Synthesis. 2nd ed. Wiley; New York: 1997

For selected representative books and reports, see:

7a Ojima I In The Chemistry of Organic Silicon Compounds . Vol. 1. Patai S, Rappoport Z. Wiley; Chichester: 1989
7b Pukhnarevich VB, Lukevics E, Kopylova LT, Voronkov MG In Perspectives of Hydrosilylation . Lukevics E. Institute of Organic Synthesis; Riga: 1992
7c Brook MA In Silicon in Organic, Organometallic, and Polymer Chemistry. Wiley; New York: 2000
7d Nishiyama H In Transition Metals for Organic Synthesis . Beller M, Bolm C. Wiley-VCH; Weinheim: 2004
7e Marciniec B. Coord. Chem. Rev. 2005; 249: 2374
7f Riant O In Modern Reduction Methods . Anderson PG, Munslow IJ. Wiley-VCH; Weinheim: 2008: 321
7g Arena CG. Mini Rev. Org. Chem. 2009; 6: 159
7h Nishiyama H In Comprehensive Chirality . Vol. 5. Carreira EM, Yamamoto H. Elsevier; Amsterdam: 2012: 318

For representative examples, see:

8a Kennedy-Smith JJ, Nolin KA, Gunterman HP, Toste FD. J. Am. Chem. Soc. 2003; 125: 4056
8b Nolin KA, Ahn RW, Toste FD. J. Am. Chem. Soc. 2005; 127: 12462
8c Abbina S, Bian S, Oian C, Du G. ACS Catal. 2013; 3: 678
8d Zhou S, Junge K, Addis D, Das S, Beller M. Angew. Chem. Int. Ed. 2009; 48: 9507
8e Misal Castro LC, Sortais J.-B, Darcel C. Chem. Commun. 2012; 48: 151
8f Lipshutz BH, Shimizu H. Angew. Chem. Int. Ed. 2004; 43: 2228
8g Volkov A, Tinnis F, Slagbrand T, Pershagen I, Adolfsson H. Chem. Commun. 2014; 50: 14508
8h Sunada Y, Kawakami H, Imaoka T, Motoyama Y, Nagashima H. Angew. Chem. Int. Ed. 2009; 48: 9511
8i Das S, Wendt B, Möller K, Junge K, Beller M. Angew. Chem. Int. Ed. 2012; 51: 1662

9 Mizuta T, Sakaguchi S, Ishii Y. J. Org. Chem. 2005; 70: 2195

10a Sousa SC. A, Fernandes AC. Adv. Synth. Catal. 2009; 352: 2218
10b Bernardo JR, Sousa SC. A, Florindo PR, Wolff M, Machura B, Fernandes AC. Tetrahedron 2013; 69: 9145
10c Das BG, Ghorai P. Org. Biomol. Chem. 2013; 11: 4379

11 Zheng J, Roisnel T, Darcel C, Sortais J.-B. ChemCatChem 2013; 5: 2729
12 Enthaler S. Catal. Lett. 2011; 141: 55

13a Enthaler S. ChemCatChem 2010; 2: 1411
13b Jaafar H, Li H, Misal Castro LC, Zheng J, Roisnel T, Dorcet V, Sortais J.-B, Darcel C. Eur. J. Inorg. Chem. 2012; 3546

14 Li B, Sortais J.-B, Darcel C, Dixneuf PH. ChemSusChem 2012; 5: 396

15a Li B, Bheeter CB, Darcel C, Dixneuf PH. ACS Catal. 2011; 1: 1221
15b Li B, Bheeter CB, Darcel C, Dixneuf PH. Top. Catal. 2014; 57: 833

16a Nishibayashi Y, Takei I, Uemura S, Hidai M. Organometallics 1998; 17: 3420
16b Hashimoto H, Aratani I, Kabuto C, Kira M. Organometallics 2003; 22: 2199

17 Li B, Sortais J.-B, Darcel C. Chem. Commun. 2013; 49: 3691
18 Tuttle T, Wang D, Thiel W, Köhler J, Hofmann M, Weis J. Dalton Trans. 2009; 5894
19 Cui X, Zhang Y, Shi F, Deng Y. Chem. Eur. J. 2011; 17: 2581
20 Zhou W, Fan M, Yin J, Jiang Y, Ma D. J. Am. Chem. Soc. 2015; 137: 11942
21 Zhao Y, Foo SW, Saito S. Angew. Chem. Int. Ed. 2011; 50: 3006
22 Zhan L.-W, Han L, Xing P, Jiang B. Org. Lett. 2015; 17: 5990
23 Motoyama Y, Taguchi M, Desmira N, Yoon S.-H, Mochida I, Nagashima H. Chem. Asian J. 2014; 9: 71
24 Sorribes I, Junge K, Beller M. J. Am. Chem. Soc. 2014; 136: 14314
25 Lepley AR, Becker RH, Guimanini AG. J. Org. Chem. 1971; 36: 1222
26 Sueki S, Kuninobu Y. Org. Lett. 2013; 15: 1544
27 Numata M, Tamesue S, Fujisawa T, Haraguchi S, Hasegawa T, Bae A.-H, Li C, Sakurai K, Shinkai S. Org. Lett. 2006; 8: 5533
28 Kovalenko OO, Volkov A, Adolfsson H. Org. Lett. 2015; 17: 446
29 Nayal OS, Bhatt V, Sharma S, Kumar N. J. Org. Chem. 2015; 80: 5912

Supplementary Material

Supporting Information (PDF)

Efficient Ruthenium(II)-Catalyzed Direct Reductive Amination of Aldehydes under Mild Conditions Using Hydrosilane as the Reductant­

Authors

Efficient Ruthenium(II)-Catalyzed Direct Reductive Amination of Aldehydes under Mild Conditions Using Hydrosilane as the Reductant