Tin(II) Compounds as Catalysts for the Kabachnik-Fields Reaction under Solvent-Free Conditions: Facile Synthesis of α-Aminophosphonates

Abstract

In the presence of a catalytic amount of tin(II) salts, the three-component Kabachnik-Fields reaction involving aldehydes, amines, and diethyl phosphite proceeded smoothly to afford the corresponding α-aminophosphonates in good to high yields. These reactions were carried out under solvent-free conditions.

α-aminophosphonates - catalysis - imines - Lewis acids - solvent-free

References

1 Horiguchi M. Kandatsu M. Nature  1959,  184:  901 

2 Alonso E. Alonso E. Solis A. del Pozo C. Synlett  2000,  698 

3 Allenberger F. Klare IJ. J. Antimicrob. Chemother.  1999,  43:  211 

4 Kafarski P. Lejczak B. Phosphorus, Sulfur Silicon Relat. Elem.  1991,  63:  193 

5 Natchev IA. Liebigs Ann. Chem.  1988,  861 

6 Chung S.-K. Kang D.-H. Tetrahedron: Asymmetry  1996,  7:  21 

7 Schlemminger I. Willecke A. Maison W. Koch R. Lutzen A. Martens J. J. Chem. Soc., Perkin Trans. 1  2001,  2804 

8 Laschat S. Kunz H. Synthesis  1992,  90 

9 Yadav JS. Reddy BVS. Raj KS. Reddy KB. Prassad AR. Synthesis  2001,  2277 

10 Matveeva ED. Zefirov NS. Russ. J. Org. Chem.  2006,  42:  1237 

11 Manjula A. Rao BV. Neelakantan P. Synth. Commun.  2003,  33:  2963 

12 Atmani A. Combret J.-C. Malhiac C. Mulengi JK. Tetrahedron Lett.  2000,  41:  6045 

13 Zefirov NS. Matveeva ED. ARKIVOC  2008,  (i):  1 

14 Qian C. Huang T. J. Org. Chem.  1998,  63:  4125 

15 Paraskar AS. Sudalai A. ARKIVOC  2006,  (x):  183 

16 Heydari A. Afsaneh A. Catal. Commun.  2007,  8:  1023 

17 Ranu BC. Hajra A. Jana U. Org. Lett.  1999,  1:  1141 

18 Xu F. Luo Y. Deng M. Shen Q. Eur. J. Org. Chem.  2003,  4728 

19 Heydari A. Zarei M. Alijanianzadeh R. Tavakol H. Tetrahedron Lett.  2001,  42:  3629 

20 Kaboudin B. Nazari R. Tetrahedron Lett.  2001,  42:  8211 

21 Hosseni-Savrari M. Tetrahedron  2008,  64:  5459 

22 Chandrasekhar S. Prakash SJ. Jagadeshwar V. Narsihmulu Ch. Tetrahedron Lett.  2001,  42:  5561 

23 Baghat S. Chakraborti A. J. Org. Chem.  2007,  72:  1263 

24 Firouzabadi H. Iranpoor N. Sobhani S. Synthesis  2004,  16:  2692 

25 Kabachnik MM. Zobnina EV. Beletskaya IP. Synlett  2005,  1393 

26 Hjeresen DL. Schutt DL. Boese JM. J. Chem. Educ.  2000,  77:  1543 

27 Wu J. Sun W. Xia H.-G. Sun X. Org. Biomol. Chem.  2006,  4:  1663 

28 Cherkasov RA. Galkin VI. Russ. Chem. Rev.  1998,  67:  857 

28In general, the mechanism involving aniline or its derivatives were determined to proceed through the attack of the imine intermediate by dialkyl phosphite. Those involving the more basic aliphatic amines may proceed through substitution of the hydroxyphosphonate intermediate by the amine, the former species forming from the reaction of the carbonyl compound with the dialkyl phosphite. This mechanism is refuted by Matveeva and Zefirov.^²9a

Some studies involving the mechanism of the Kabachnik-Fields reaction include:

29a Matveeva ED. Zefirov NS. Dokl. Chem.  2008,  420:  137 

29b Galkina IV. Galkin VI. Cherkasov RA. Russ. J. Gen. Chem.  1998,  68:  1402 

29c Galkina IV. Sobanov AA. Galkin VI. Cherkasov RA. Russ. J. Gen. Chem.  1998,  68:  1398 

29d Galkina IV. Zvereva ER. Galkin VI. Cherkasov RA. Russ. J. Gen. Chem.  1998,  68:  1391 

29e Galkina IV. Zvereva ER. Galkin VI. Sobanov AA. Cherkasov RA. Russ. J. Gen. Chem.  1998,  68:  1387 

29f Krutikov VI. Lavren"ev AN. Sukhanovskaya EV. Zh. Obshch. Khim.  1991,  61:  3121 

30

Lewis acids such as SnCl₂ may not be necessary in the formation of aminophosphonate 3f, which involves piperidine, a secondary aliphatic amine. We are currently investigating the synthesis of α-aminophosphonates from secondary aliphatic amines.

31 Azizi N. Saidi MR. Tetrahedron  2003,  59:  5329 

32 Sun P. Yang X. Hu Z. J. Chem. Res.  2006,  4:  240