Synlett 2014; 25(09): 1295-1298
DOI: 10.1055/s-0033-1341250
letter
© Georg Thieme Verlag Stuttgart · New York

Highly Efficient Rhodium-Catalyzed Transfer Hydrogenation of Nitroarenes into Amines and Formanilides

Yawen Wei
a   Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, P. R. of China   Fax: +86(29)81530727   Email: c.wang@snnu.edu.cn
,
Jianjun Wu
b   Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK   Email: j.xiao@liv.ac.uk
,
Dong Xue
a   Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, P. R. of China   Fax: +86(29)81530727   Email: c.wang@snnu.edu.cn
,
Chao Wang*
a   Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, P. R. of China   Fax: +86(29)81530727   Email: c.wang@snnu.edu.cn
,
Zhaotie Liu
a   Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, P. R. of China   Fax: +86(29)81530727   Email: c.wang@snnu.edu.cn
,
Zhuozhuo Zhang
a   Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, P. R. of China   Fax: +86(29)81530727   Email: c.wang@snnu.edu.cn
,
Guangfu Chen
a   Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, P. R. of China   Fax: +86(29)81530727   Email: c.wang@snnu.edu.cn
,
Jianliang Xiao*
a   Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, P. R. of China   Fax: +86(29)81530727   Email: c.wang@snnu.edu.cn
b   Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK   Email: j.xiao@liv.ac.uk
› Author Affiliations
Further Information

Publication History

Received: 02 February 2014

Accepted after revision: 25 March 2014

Publication Date:
29 April 2014 (online)


Abstract

An efficient and selective rhodium-catalyzed transfer hydrogenation of nitroarenes with formic acid as the hydrogen source to give amines or formanilides has been developed. The addition of iodide ion accelerates the reaction, which can take place at room temperature.

Supporting Information

 
  • References

    • 1a Downing RS, Kunkeler PJ, van Bekkum H. Catal. Today 1997; 37: 121
    • 1b Ono N. The Nitro Group in Organic Synthesis . Wiley-VCH; New York: 2001
    • 2a Blaser HU. Science 2006; 313: 312
    • 2b Blaser HU, Steiner H, Studer M. ChemCatChem 2009; 1: 210
    • 2c Wang X, Liang M, Zhang J, Wang Y. Curr. Org. Chem. 2007; 11: 299
    • 2d Chen Y, Qiu J, Wang X, Xiu J. J. Catal. 2006; 242: 227
    • 2e Corma A, Serna P. Science 2006; 313: 332
    • 2f Corma A, Serna P, Concepción P, Calvino JJ. J. Am. Chem. Soc. 2008; 130: 8748
    • 2g Kantam ML, Chakravarti R, Pal U, Sreedhar B, Bhargava S. Adv. Synth. Catal. 2008; 350: 822
    • 2h Takasaki M, Motoyama Y, Higashi K, Yoon S.-H, Mochida I, Nagashima H. Org. Lett. 2008; 10: 1601
    • 2i Corma A, González-Arellano C, Iglesias M, Sánchez F. Appl. Catal., A 2009; 356: 99
    • 2j Fan GY, Zhang L, Fu HY, Yuan ML, Li RX, Chen H, Li XJ. Catal. Commun. 2010; 11: 451
    • 3a Lauwiner M, Rys P, Wissmann J. Appl. Catal., A 1998; 172: 141
    • 3b Rahaim RJ, Maleczka RE. Org. Lett. 2005; 7: 5087
    • 3c Junge K, Wendt B, Shaikh N, Beller M. Chem. Commun. 2010; 46: 1769
    • 3d Sharma U, Kumar P, Kumar N, Kumar V, Singh B. Adv. Synth. Catal. 2010; 352: 1834
    • 3e Kadam HK, Tilve SG. RSC Adv. 2012; 2: 6057
    • 3f Layek K, Kantam ML, Shirai M, Nishio-Hamane D, Sasaki T, Maheswaran H. Green Chem. 2012; 14: 3164
    • 3g Luo P, Xu K, Zhang R, Huang L, Wang J, Xing W, Huang J. Catal. Sci. Technol. 2012; 2: 301
    • 3h Kelly SM, Lipshutz BH. Org. Lett. 2013; 16: 98
    • 3i Park S, Lee IS, Park J. Org. Biomol. Chem. 2013; 11: 395
    • 4a Zassinovich G, Mestroni G, Gladiali S. Chem. Rev. 1992; 92: 1051
    • 4b Noyori R, Hashiguchi S. Acc. Chem. Res. 1997; 30: 97
    • 4c Palmer MJ, Wills M. Tetrahedron: Asymmetry 1999; 10: 2045
    • 4d Wills M, Palmer M, Smith A, Kenny J, Walsgrove T. Molecules 2000; 5: 4
    • 4e Everaere K, Mortreux A, Carpentier JF. Adv. Synth. Catal. 2003; 345: 67
    • 4f Clapham SE, Hadzovic A, Morris RH. Coord. Chem. Rev. 2004; 248: 2201
    • 4g Gladiali S, Alberico E. Chem. Soc. Rev. 2006; 35: 226
    • 4h Samec JS. M, Backvall JE, Andersson PG, Brandt P. Chem. Soc. Rev. 2006; 35: 237
    • 4i Ikariya T, Blacker AJ. Acc. Chem. Res. 2007; 40: 1300
    • 4j Wu X, Xiao J. Chem. Commun. 2007; 2449
    • 4k Wang C, Wu X, Xiao J. Chem. Asian J. 2008; 3: 1750
    • 4l Wu XF, Wang C, Xiao JL. Platinum Met. Rev. 2010; 54: 3
    • 5a Sharf VZ, Freidlin LK, Savchenko BM, Krutii VN. Russ. Chem. Bull. 1979; 28: 1061
    • 5b Jagadeesh RV, Wienhöfer G, Westerhaus FA, Surkus A.-E, Junge H, Junge K, Beller M. Chem. Eur. J. 2011; 17: 14375
    • 5c Imai H, Nishiguchi T, Fukuzumi K. Chem. Lett. 1976; 5: 655
    • 5d Watanabe Y, Ohta T, Tsuji Y, Hiyoshi T, Tsuji Y. Bull. Chem. Soc. Jpn. 1984; 57: 2440
    • 5e The Khai B, Arcelli A. J. Organomet. Chem. 1986; 309: C63
    • 5f Wienhöfer G, Sorribes I, Boddien A, Westerhaus F, Junge K, Junge H, Llusar R, Beller M. J. Am. Chem. Soc. 2011; 133: 12875
    • 5g Sorribes I, Wienhöfer G, Vicent C, Junge K, Llusar R, Beller M. Angew. Chem. Int. Ed. 2012; 51: 7794
  • 6 Wu J, Wang C, Tang W, Pettman A, Xiao J. Chem. Eur. J. 2012; 18: 9525
    • 7a Pratap TV, Baskaran S. Tetrahedron Lett. 2001; 42: 1983
    • 7b Kamal A, Srinivasa Reddy K, Rajendra Prasad B, Hari Babu A, Ramana AV. Tetrahedron Lett. 2004; 45: 6517
    • 7c Rahman M, Kundu D, Hajra A, Majee A. Tetrahedron Lett. 2010; 51: 2896
    • 7d Lou XB, He L, Qian Y, Liu YM, Cao Y, Fan KN. Adv. Synth. Catal. 2011; 353: 281
    • 8a Pettit G, Kalnins M, Liu T, Thomas E, Parent K. J. Org. Chem. 1961; 26: 2563
    • 8b Kotachi S, Tsuji Y, Kondo T, Watanabe Y. J. Chem. Soc., Chem. Commun. 1990; 549
    • 8c Jackson A, Meth-Cohn O. J. Chem. Soc., Chem. Commun. 1995; 1319
  • 9 Arylformamides 3an; General Procedure Nitroarene 1 (1.6 mmol), KI (1.6 mmol), [Cp*RhCl2]2 (0.0016 mmol), and a magnetic stirrer bar were placed in a carousel tube, and DMSO, HCO2H (32 mmol), and Et3N (10.7 mmol) were added by injection. The mixture was bubbled with argon for 15 min at r.t. then stirred under argon at 100 °C for 20 h. The mixture was cooled to r.t., basified with sat. aq NaOH, and extracted with CH2Cl2 (5 × 3 mL). The organic layers were combined, washed with brine, dried (Na2SO4), and concentrated. The residue was purified by flash chromatography (PE–EtOAc).
  • 10 Wei YW, Xue D, Lei Q, Wang C, Xiao JL. Green Chem. 2013; 15: 629