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.

Key words

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 
• 31 Azizi N. Saidi MR. Tetrahedron  2003,  59:  5329 
• 32 Sun P. Yang X. Hu Z. J. Chem. Res.  2006,  4:  240 

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.