Synthesis 2013; 45(22): 3147-3150
DOI: 10.1055/s-0033-1339712
paper
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Synthesis of α-Aminophosphonate Esters by the Addition of Dialkyl Phosphites to tert-Butanesulfinyl Imines

Hasan A. Khan
Department of Chemistry, Yale University, New Haven, CT 06520, USA   Email: jonathan.ellman@yale.edu
,
Jonathan A. Ellman*
Department of Chemistry, Yale University, New Haven, CT 06520, USA   Email: jonathan.ellman@yale.edu
› Author Affiliations
Further Information

Publication History

Received: 13 July 2013

Accepted after revision: 13 August 2013

Publication Date:
06 September 2013 (online)


Abstract

The KHMDS-mediated addition of dialkyl phosphites to N-tert-butanesulfinyl aldimines and ketimines proceeds in uniformly high yields and diastereoselectivities and thereby enables the rapid and general asymmetric synthesis of α-aminophosphonate esters.

Supporting Information

 
  • References

    • 1a Freeman M. Annu. Rev. Genet. 2008; 42: 191
    • 1b Urban S. Genes Dev. 2006; 20: 3054
  • 2 Xue Y, Chowdury S, Liu X, Akiyama Y, Ellman J, Ya H. Biochemistry 2012; 51: 3723

    • For leading references on the synthesis and bioactivity of aminophosphonate derivatives, see:
    • 3a Ordóñez M, Rojas-Cabrera H, Cativiela C. Tetrahedron 2009; 65: 17
    • 3b Kafarski P, Lejczak B. Curr. Med. Chem. Anti-Cancer Agents 2001; 1: 301
    • 3c Aminophosphonic and Aminophosphinic Acids: Chemistry and Biological Activities. Kukhar VP, Hudson HR. Wiley; New York: 2000
    • 3d Sampson NS, Bartlett PA. Biochemistry 1991; 30: 2255

      For recent reviews on asymmetric amine synthesis using tert-butanesulfinamide, see:
    • 4a Robak MT, Herbage MA, Ellman JA. Chem. Rev. 2010; 110: 3600
    • 4b Ferreira F, Botuha C, Chemla F, Perez-Luna A. Chem. Soc. Rev. 2009; 38: 1162

      For general reviews on applications of a broader range of sulfinamides, see:
    • 5a Davis FA. J. Org. Chem. 2006; 71: 8993
    • 5b Morton D, Stockman RA. Tetrahedron 2006; 62: 8869
    • 5c Senanayake CH, Krishnamurthy D, Lu Z.-H, Han Z, Gallou I. Aldrichimica Acta 2005; 38: 93
    • 7a Mikołajczyk M, Łyżwa P, Drabowicz J. Tetrahedron: Asymmetry 1997; 8: 3991
    • 7b Lefebvre IM, Evans SA. J. Org. Chem. 1997; 62: 7532
    • 7c Davis FA, Lee S, Yan H, Titus DD. Org. Lett. 2001; 3: 1757
    • 7d Davis FA, Prasad KR. J. Org. Chem. 2003; 68: 7249
    • 7e Łyżwa P, Błaszczyk J, Sieroń L, Mikołajczyk M. Eur. J. Org. Chem. 2013; 2106
  • 8 Smith AB, Yager KM, Taylor CM. J. Am. Chem. Soc. 1995; 117: 10879
  • 9 Brak K, Barrett KT, Ellman JA. J. Org. Chem. 2009; 74: 3606
  • 10 Soroka M, Zygmunt J. Synthesis 1988; 301
  • 11 Verbrugghen T, Vandurm P, Pouyez J, Maes L, Wouters J, Van Calenbergh S. J. Med. Chem. 2013; 56: 376
  • 12 Liu G, Cogan DA, Owens TD, Tang TP, Ellman JA. J. Org. Chem. 1999; 64: 1278