A New and Convenient Asymmetric Synthesis of α-Amino- and α-Alkyl-α-aminophosphonic Acids Using N-tert-Butylsulfinyl Imines as Chiral Auxiliaries

Abstract

Nucleophilic addition of dialkyl phosphites to N-tert-butylsulfinyl aldimines or ketimines occurs successfully at room temperature with potassium carbonate as base to afford α-amino- and α-alkyl-α-amino-N-(tert-butylsulfinyl)phosphonates in good to excellent chemical yield and diastereoselectivity. The major diastereo­mers were separated and smoothly converted into enantiopure α-amino- and α-alkyl-α-aminophosphonic acids.

Key words

α-aminophosphonic acids - α-alkyl-α-aminophosphonic acids - N-tert-butylsulfinyl imines - asymmetric synthesis - nucleophilic addition

References

• 1 Aminophosphonic and Aminophosphinic Acids: Chemistry and Biological Activities   Kukhar VP. Hudson HR. Wiley & Sons; New York: 2000. 
• 2 For general references, see: Lin GQ. Li YM. Chen ASC. Principles and Applications of Asymmetric Synthesis   Wiley & Sons; New York: 2001. 
• 3 Kolodiazhnyi OI. Tetrahedron: Asymmetry  1998,  9:  1279 
• 4 Kirst HA. Yeh WK. Zmijewski MJ. Enzyme Technologies for Pharmaceutical and Biotechnological Applications   Marcel Dekker; New York/Basel: 2001. 
• 5a Sasai H. Arai S. Tahara Y. Shibasaki M. J. Org. Chem.  1995,  60:  6656 
• 5b Dalko PI. Moisan L. Angew. Chem. Int. Ed.  2004,  43:  5138 
• 5c Joly GD. Jacobsen EN. J. Am. Chem. Soc.  2004,  126:  4102 
• 5d Bernardi L. Zhuang W. Jørgensen KA. J. Am. Chem. Soc.  2005,  127:  5772 
• 5e Pettersen D. Marcolini M. Bernardi L. Fini F. Herrera RP. Sgarzani V. Ricci A. J. Org. Chem.  2006,  71:  6269 
• 5f Saito B. Eagmi H. Katsuki T. J. Am. Chem. Soc.  2007,  129:  1978 
• 6 Gilmore WF. McBride HA. J. Am. Chem. Soc.  1972,  94:  4361 
• 7 Yuan CY. Cui SH. Phosphorus, Sulfur Silicon Relat. Elem.  1991,  55:  159 
• 8 Davis FA. Chen B.-C. Chem. Soc. Rev.  1998,  27:  13 
• 9 Liu G. Cogan DA. Ellman JA. J. Am. Chem. Soc.  1997,  119:  9913 
• 10a Davis FA. Fanelli DL. J. Org. Chem.  1998,  63:  1981 
• 10b Davis FA. Szewczyk JM. Tetrahedron Lett.  1998,  39:  5951 
• 11a Lefebvre IM. Evans SA. J. Org. Chem.  1997,  62:  7532 
• 11b Mikoajczyk M. Łyżwa P. Drabowicz J. Tetrahedron: Asymmetry  1997,  8:  3991 
• 11c Davis FA. Lee S. Yan H. Titus DD. Org. Lett.  2001,  3:  1757 
• 11d Mikoajczyk M. Łyżwa P. Drabowicz J. Tetrahedron: Asymmetry  2002,  13:  2571 
• 11e Davis FA. Prasad KR. J. Org. Chem.  2003,  68:  7249 
• 12 Mikoajczyk M. Łyżwa P. Drabowicz J. Wieczorek MW. Baszczyk J. Chem. Commun.  1996,  1503 
• 13a Davis FA. McCoull W. Tetrahedron Lett.  1999,  40:  249 
• 13b Davis FA. Reddy GV. Liu H. J. Am. Chem. Soc.  1995,  117:  3651 
• 14 Ellman JA. Owens TD. Tang TP. Acc. Chem. Res.  2002,  35:  984 
• 15 Davis FA. Lee S. Zhang H. Fanelli DL. J. Org. Chem.  2000,  65:  8704