Synlett 2014; 25(19): 2717-2720
DOI: 10.1055/s-0034-1379102
cluster
© Georg Thieme Verlag Stuttgart · New York

CAN-Catalyzed Rapid C–O Bond Formation towards α-Aminoxylation of Ketones

Peng Feng
a  State Key Laboratory of Natural and Biomimetic Drugs, Peking University, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191, P. R. of China   Fax: +86(10)82805297   Email: jiaoning@bjmu.edu.cn
,
Song Song
a  State Key Laboratory of Natural and Biomimetic Drugs, Peking University, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191, P. R. of China   Fax: +86(10)82805297   Email: jiaoning@bjmu.edu.cn
,
Li-He Zhang
a  State Key Laboratory of Natural and Biomimetic Drugs, Peking University, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191, P. R. of China   Fax: +86(10)82805297   Email: jiaoning@bjmu.edu.cn
,
Ning Jiao*
a  State Key Laboratory of Natural and Biomimetic Drugs, Peking University, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191, P. R. of China   Fax: +86(10)82805297   Email: jiaoning@bjmu.edu.cn
b  Shanghai Key Laboratory of Green Chemistry and Chemical Processes, East China Normal University, Shanghai 200062, P. R. of China
› Author Affiliations
Further Information

Publication History

Received: 03 July 2014

Accepted after revision: 18 August 2014

Publication Date:
02 October 2014 (online)

Abstract

A simple and efficient approach towards α-oxyaminated ketones has been developed through CAN-catalyzed C–O bond formation with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). The environmentally friendly transformation is practical due to the use of commercial available catalyst, easy operating procedures, the broad substrate scope, and short reaction time.

Supporting Information

 
  • References

    • 1a Hawker CJ, Bosmann AW, Harth E. Chem. Rev. 2001; 101: 3661
    • 1b Benoit D, Grimaldi S, Robin S, Finet JP, Tordo P, Gnanou Y. J. Am. Chem. Soc. 2000; 122: 5929
    • 1c Benoit D, Chaplinski V, Braslau R, Hawker CJ. J. Am. Chem. Soc. 1999; 121: 3904
    • 2a Pfaendner RC. R. C. R. Chim. 2006; 9: 1338
    • 2b Schoening K.-U, Fischer W, Hauck S, Dichtl A, Kuepfert M. J. Org. Chem. 2009; 74: 1567
    • 2c Janey JM. Angew. Chem. Int. Ed. 2005; 44: 4292
    • 2d Marigo M, Jørgensen KA. Chem. Commun. 2006; 2001
    • 2e Studer A. Chem. Soc. Rev. 2004; 33: 267
    • 2f Studer A. Angew. Chem. Int. Ed. 2000; 39: 1108

      For selected reviews and examples for the preparation of alkoxyamines, see:
    • 3a Braslau R, Naik N, Zipse H. J. Am. Chem. Soc. 2000; 122: 8421
    • 3b Jahn U, Müller M, Aussieker S. J. Am. Chem. Soc. 2000; 122: 5212
    • 3c Tebben L, Studer A. Angew. Chem. Int. Ed. 2011; 50: 5034
    • 3d Braslau R, Burrill LC, Mahal LK, Wedekind T. Angew. Chem., Int. Ed. Engl. 1997; 36: 237
    • 3e Humbeck JF. V, Simonovich SP, Knowles RR, Macmillan DW. C. J. Am. Chem. Soc. 2010; 132: 10012
    • 3f Simonovich SP, Van Humbeck JF, Macmillan DW. C. Chem. Sci. 2012; 3: 58
    • 3g Zhong G. Angew. Chem. Int. Ed. 2003; 42: 4247
    • 3h Sibi MP, Hasegawa M. J. Am. Chem. Soc. 2007; 129: 4124
    • 3i Li Y, Pouliot M, Vogler T, Renaud P, Studer A. Org. Lett. 2012; 14: 4474
    • 3j Kano T, Mii H, Maruoka K. Angew. Chem. Int. Ed. 2010; 49: 6638
    • 4a Schämann M, Schäfer HJ. Synlett 2004; 1601
    • 4b For treatment of silyl enol ether with oxoammonium salt, see: Hayashi M, Shibuya M, Iwabuchi Y. Org. Lett. 2012; 14: 154
    • 5a Jahn U, Hartmann P, Dix I, Jones PG. Eur. J. Org. Chem. 2001; 3333
    • 5b Dinca E, Hartmann P, Smrček J, Dix I, Jones PG, Jahn U. Eur. J. Org. Chem. 2012; 4461
    • 5c Jahn U. J. Org. Chem. 1998; 63: 7130
    • 5d Braslau R, Burrill LC. II, Siano M, Naik N, Howden RK, Mahal LK. Macromolecules 1997; 30: 6445

      For examples on the application of photochemistry in α-aminoxylation of ketones, see:
    • 6a Liu H, Feng W, Kee CW, Zhao Y, Leow D, Pan Y, Tan C.-H. Green Chem. 2010; 12: 953
    • 6b Takashi K, Yusuke Y, Munetaka A. Chem. Lett. 2012; 41: 999

      For recent advance in α-aminoxylation of ketones, see:
    • 7a Mabe PJ, Zakarian A. Org. Lett. 2014; 16: 516
    • 7b Xie Y.-X, Song R.-J, Liu Y, Liu Y.-Y, Xiang J.-N, Li J.-H. Adv. Synth. Catal. 2013; 355: 3387
  • 8 Typical Procedure for the Synthesis of 1,3-Diphenyl-2-[(2,2,6,6-tetramethylpiperidin-1-yl)oxy]propane-1,3-dione (2a)6b CAN (32.6 mg, 0.06 mmol), TEMPO (46.8 mg, 0.3 mmol), and 1a (67.2 mg, 0.3 mmol) in EtOAc (3.0 mL) was mixed under air. The mixture was stirred at 60 °C for 10–30 min using TLC detection with iodine. After cooling down and concentrating in vacuum, the residue was purified by flash chromatography on silica gel (eluent: PE–EtOAc, 30:1) to afford 102.5 mg (90%) of 2a. Analytical Data for Compound 2a Solid. 1H NMR (400 MHz, CDCl3): δ = 8.19 (d, J = 7.8 Hz, 4 H), 7.56–7.54 (m, 2 H), 7.53–7.43 (m, 4 H), 6.29 (s, 1 H), 1.48–1.38 (m, 6 H), 1.13 (s, 6 H), 0.95 (s, 6 H). 13C NMR (100 MHz, CDCl3): δ = 195.0, 134.7, 133.7, 130.2, 128.4, 99.1, 60.2, 40.1, 32.9, 20.2, 17.0. MS (EI): m/z = 379.2 (100) [M]+.
    • 9a Wetter C, Jantos K, Woithe K, Studer A. Org. Lett. 2003; 5: 2899
    • 9b Schulte B, Studer A. Synthesis 2006; 2129
    • 10a Laugier J, Latour J, Caneschi A, Rey P. Inorg. Chem. 1991; 30: 4474
    • 10b Pervukhina NV, Romanenko GV, Podberezskaya NV. J. Struct. Chem. 1994; 35: 367
    • 10c Dijksman A, Arends IW. C. E, Sheldon RA. Org. Biomol. Chem. 2003; 1: 3232
    • 10d Feng P, Sun X, Su Y, Li X, Zhang L.-H, Shi X, Jiao N. Org. Lett. 2014; 16: 3388