Synlett 2019; 30(01): 73-76
DOI: 10.1055/s-0037-1611364
letter
© Georg Thieme Verlag Stuttgart · New York

Cesium Carbonate-Promoted P-Alkylation of Phosphinecarboxamides

Xing-Guo Chen
a  College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070, P. R. of China
b  Gansu International Scientific and Technological Cooperation Base of Water-Retention Chemical Functional Materials, Lanzhou, 730070, P. R. of China   Email: quanzhengjun@hotmail.com
,
Qiu-Li Wu
a  College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070, P. R. of China
b  Gansu International Scientific and Technological Cooperation Base of Water-Retention Chemical Functional Materials, Lanzhou, 730070, P. R. of China   Email: quanzhengjun@hotmail.com
,
Fei Hou
a  College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070, P. R. of China
b  Gansu International Scientific and Technological Cooperation Base of Water-Retention Chemical Functional Materials, Lanzhou, 730070, P. R. of China   Email: quanzhengjun@hotmail.com
,
Xi-Cun Wang
a  College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070, P. R. of China
b  Gansu International Scientific and Technological Cooperation Base of Water-Retention Chemical Functional Materials, Lanzhou, 730070, P. R. of China   Email: quanzhengjun@hotmail.com
,
Zheng-Jun Quan*
a  College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070, P. R. of China
b  Gansu International Scientific and Technological Cooperation Base of Water-Retention Chemical Functional Materials, Lanzhou, 730070, P. R. of China   Email: quanzhengjun@hotmail.com
› Author Affiliations
We are thankful for the financial support from the National Nature Science Foundation of China (No 21562036), and the Scientific and Technological Innovation Engineering program of Northwest Normal University (NWNU-LKQN-15-1).
Further Information

Publication History

Received: 09 October 2018

Accepted after revision: 31 October 2018

Publication Date:
03 December 2018 (online)


Abstract

An effective method for the P-alkylation of N-arylphosphinecarboxamides was demonstrated. Primary N-arylphosphinecarboxamides without additional protection underwent P-monoalkylation with various alkyl halides in the presence of cesium carbonate as a promoter. The reactivity of phosphinecarboxamides was also explored.

Supporting Information

 
  • References and Notes

    • 1a De Clercq E. Med. Res. Rev. 2011; 31: 118
    • 1b Katti KV, Gali H, Smith CJ, Berning DE. Acc. Chem. Res. 1999; 32: 9
    • 1c Queffélec C, Petit M, Janvier P, Knight DA, Bujoli B. Chem. Rev. 2012; 112: 3777
    • 1d McManus HA, Guiry PJ. Chem. Rev. 2004; 104: 4151
    • 1e Weber L. Angew. Chem. Int. Ed. 2002; 41: 563 ; Angew. Chem. 2002, 114, 583
    • 1f Fleming JT, Higham LJ. Coord. Chem. Rev. 2015; 297: 127
    • 1g Meeuwissen J, Detz R, Sandee AJ, de Bruin B, Siegler MA, Spek AL, Reek JN. H. Eur. J. Inorg. Chem. 2010; 2992
    • 1h Clarke TP, Landis CR. Tetrahedron: Asymmetry 2004; 15: 2123
  • 2 Jupp AR, Goicoechea JM. J. Am. Chem. Soc. 2013; 135: 19131
  • 3 Faria EN, Jupp AR, Goicoechea JM. Chem. Commun. 2017; 53: 7092
  • 4 Robinson TP, Goicoechea JM. Chem. Eur. J. 2015; 21: 5727
  • 5 Geeson MB, Jupp AR, McGrady JE, Goicoechea JM. Chem. Commun. 2014; 50: 12281
  • 6 Beddoe SV. F, Cosham SD, Kulak AN, Jupp AR, Goicoechea JM, Hyett G. Dalton Trans. 2018; 47: 9221
  • 7 Quin LD. A Guide to Organophosphorus Chemistry . Wiley- Interscience; New York: 2000
  • 9 Imamoto T, Oshiki T, Onozawa T, Kusumoto T, Sato K. J. Am. Chem. Soc. 1990; 112: 5244
    • 10a Lebel H, Morin S, Paquet V. Org. Lett. 2003; 5: 2347
    • 10b Blank NF, McBroom KC, Glueck DS, Kassel WS, Rheingold AL. Organometallics 2006; 25: 1742
    • 10c Anderson BJ, Guino-o MA, Glueck DS, Golen JA, DiPasquale AG, Liable-Sands LM, Rheingold AL. Org. Lett. 2008; 10: 4425
  • 11 Stewart B, Harriman A, Higham LJ. Organometallics 2011; 30: 5338
  • 12 Wu Y.-H, Li Z.-F, Wang W.-P, Wang X.-C, Quan Z.-J. Eur. J. Org. Chem. 2017; 5546
  • 13 Phosphinecarboxamides 3aq; General Procedure The appropriate N-arylphosphinecarboxamide 1 (0.2 mmol) and haloalkane 2 (0.24 mmol, 1.2 equiv) were added to a sealed tube charged with a mixture of Cs2CO3 (0.2 mmol, 1 equiv) in DMSO (4 mL), and the resulting mixture was stirred at r.t. for 0.5 h. When the reaction was complete (TLC), H2O (30 mL) was added and the mixture was extracted with EtOAc. The organic phase was separated, dried (MgSO4), filtered, and concentrated. The crude product was purified by column chromatography [silica gel, PE–EtOAc (4:1)]. N-(4-Methoxyphenyl)-1-methylphosphinecarboxamide (3a) White solid; yield: 33 mg (85%); mp 75–76 °C. 1H NMR (600 MHz, CDCl3): δ = 7.69 (s, 1 H), 7.39 (d, J = 8.4 Hz, 2 H), 6.81 (d, J = 8.4 Hz, 2 H), 4.02 (dq, J = 206.4, 7.8 Hz, 1 H), 3.76 (s, 3 H), 1.36 (dd, J = 7.2, 3.0 Hz, 3 H). 13C NMR (150 MHz, CDCl3): δ = 176.67 (d, J = 14.6 Hz), 156.48, 131.01 (d, J = 4.1 Hz), 121.80, 114.09, 55.44, 1.10 (d, J C–P = 8.1 Hz, PCH3). 31P NMR (162 MHz, CDCl3): δ = –74.42. HRMS(ESI): m/z [M + H]+ Calcd for C9H13NO2P: 198.0678; Found: 198.0679.
  • 14 Wiedemann G. Ann. Phys. Chem. 1848; 150: 67
  • 15 Jupp AR, Trott G, Payen de la Garanderie É, Holl JD. G, Carmichael D, Goicoechea JM. Chem. Eur. J. 2015; 21: 8015
  • 16 Becker G, Hübler K, Niemeyer M, Seidler N, Thinus B. Z. Anorg. Allg. Chem. 1996; 622: 197