Synlett 2009(11): 1859-1860  
DOI: 10.1055/s-0029-1217375
SPOTLIGHT
© Georg Thieme Verlag Stuttgart ˙ New York

Synthetic Utility of N-Sulfonylimines

Davender Kumar Shukla*
Department of Chemistry, University School of Basic & Applied Sciences, Guru Gobind Singh Indraprastha University, Kashmere Gate, Delhi-110403, India.
e-Mail: dev.shukla@rediffmail.com;

Further Information

Publication History

Publication Date:
16 June 2009 (online)

Biographical Sketches

Davender Kumar Shukla was born in 1979 at Pratapgarh, Uttar Pradesh, India. He received his M.Sc. degree in 2003. Presently he is working as a university research fellow towards his Ph.D. degree under the supervision of Dr. Arif Ali Khan at Guru Gobind Singh Indraprastha University, Delhi, India. His research work is focused on metal ion catalyzed organic synthesis and the synthesis of new range of N-sulfonylimines and their applications in organic synthesis.

Introduction:

Analogous to carbon-carbon and carbon-oxygen double bonds, carbon-nitrogen double bond has been an active site of study in recent times. The reactivity of the carbon-nitrogen double bond lies in between that of the carbonyl and olefinic functions. The carbon-nitrogen double bond has an additional lone pair of electrons which leads to its distinctive properties from carbon-carbon double bond.

N-Sulfonylimine [¹] (also known as sulfonylimine) is one such good example of azomethenic carbon-nitrogen double bond. N-Sulfonylimines are useful precursors for the synthesis of important synthetic intermediates such as oxaziridines [²] and aziridines [³] as well as for the synthesis of compounds of medicinal importance. [4-5] N-Sulfonyl­imines also serves as heterodienes and heterodienophiles in [4+2] cycloadditions. [6]

Preparation:

N-Sulfonylimines can be synthesised by direct condensation of primary sulfonamides with aldehydes or ketones in the presence of some dehydrating agents (TiCl4, 4 Å molecular sieve, MgSO4, AlCl3). [²] [7-9] However, only few methods are reported for the preparation of N-Sulfonylimines of enolizable and sterically hindered ketones. Such reactions involve the in situ generation of oxime O-sulfinyl derivatives [¹0] and their subsequent homolytic rearrangement to sulfonylimines. Recently, a simple method has been reported which involves the condensation of simple as well as hindered ketones with 4-toluenesulfon­amides in the presence of TiCl4 and Et3N. [¹¹]

Scheme 1

Abstracts

(A) Catalytic hydrogenation of methyl vinyl ketone and ethyl ­vinyl ketone in the presence of N-(2-nitrophenylsulfonyl)imines at ambient pressure with tri-2-furylphosphine ligand rhodium catalysts produces the mannich product with moderate to good syn-diasteroselectivity. [¹²]

(B) Direct asymmetric mannich-type reaction of N-sulfonyl­imines with trichloromethylketone in the presence of lanthanum aryloxide and Pybox gives β-amino carbonyl compounds. [¹³]

(C) Selective reduction of electronically deficient imines in the presence of ketones, Et3Zn, and Ni(acac)2 produces respective amines in moderate to good yields. [¹4]

(D) The catalytic mannich reaction of 1,1-difluoro-2-trialkyl(aryl)-silyl-2-trimethylsilyloxyethenes with sulfonylimines gives α,α-difluoro-β-amino acid derivatives. [¹5]

(E) The reaction of phosphorylated N-sulfonylimines with hydrophosphoryl agents involve the C-N transfer of phosphoryl group and produce aza-Perkow products. [¹6]

(F) In the presence of a catalytic amount of chiral diaminothiophosphoramide the asymmetric addition of diethyl zinc to N-­sulfonylimines can be achieved in moderate to good yield ee (63-93%). [¹7]

(G) The nucleophillic addition of chiral lithium enolates of (S)-­(-)-4-benzyl-2-oxazolidinone acetamide with N-tosylarylaldehyde imines gives β-aryl-β-amino acid derivatives in good to excellent diastereoselectivity. [¹8]

    References

  • 1 Ruano JLG. Alemán J. Cid MB. Parra A. Org. Lett.  2005,  7:  179 
  • 2 Davis FA. Lamendola JF. Nadir U. Kluger EW. Sedergran TC. Panunto TW. Billmers R. Jenkins RJr. Turchi IJ. Watson WH. Chen JS. Kimura M. J. Am. Chem. Soc.  1980,  102:  2000 
  • 3 Zhou Y.-G. Li A.-H. Hou X.-L. Dai L.-X. Tetrahedron Lett.  1997,  38:  7225 
  • 4 Zhou X.-T. Lin Y.-R. Dai L.-X. Sun J. Xia L.-J. Tang M.-H. J. Org Chem.  1999,  64:  1331 
  • 5 Hayashi T. Kishi E. Soloshonok VA. Uozumi Y. Tetrahedron Lett.  1996,  37:  4969 
  • 6 Boger DL. Weinreb SM. Hetero Diels-Alder Methodology in Organic Synthesis, In Organic Chemistry   Vol. 47:  Wasserman HH. Academic Press; New York: 1987.  p.36 
  • 7 Boger DL. Corbett WL. Curran TT. Kasper AM.
    J. Am. Chem. Soc.  1991,  113:  1713 
  • 8 Jennings WB. Lovely CJ. Tetrahedron Lett.  1988,  29:  3725 
  • 9 Davis FA. Zhou P. Lal GS. Tetrahedron Lett.  1990,  31:  1653 
  • 10 Boger DL. Corbett WL. J. Org. Chem.  1992,  57:  4777 
  • 11 Ram RN. Khan AA. Synth. Commun.  2001,  31:  841 
  • 12 Garner SA. Krische MJ. J. Org. Chem.  2007,  72:  5843 
  • 13 Morimoto H. Lu G. Aoyama N. Matsunaga S. Shibasaki M. J. Am. Chem. Soc.  2007,  129:  9588 
  • 14 Xiao X. Wang H. Huang Z. Yang J. Bian X. Qin Y. Org. Lett.  2006,  8:  139 
  • 15 Chungh WJ. Omote M. Welch JT. J. Org. Chem.  2005,  70:  7784 
  • 16 Rassukana YV. Onys’ko PP. Davydova KO. Sinitsa AD. Tetrahedron Lett.  2004,  45:  3899 
  • 17 Shi M. Zhang W. Tetrahedron Asymmetry  2003,  14:  3407 
  • 18 Ma Z. Zhao Y. Jiang N. Jin X. Wang J. Tetrahedron Lett.  2002,  43:  3209 

    References

  • 1 Ruano JLG. Alemán J. Cid MB. Parra A. Org. Lett.  2005,  7:  179 
  • 2 Davis FA. Lamendola JF. Nadir U. Kluger EW. Sedergran TC. Panunto TW. Billmers R. Jenkins RJr. Turchi IJ. Watson WH. Chen JS. Kimura M. J. Am. Chem. Soc.  1980,  102:  2000 
  • 3 Zhou Y.-G. Li A.-H. Hou X.-L. Dai L.-X. Tetrahedron Lett.  1997,  38:  7225 
  • 4 Zhou X.-T. Lin Y.-R. Dai L.-X. Sun J. Xia L.-J. Tang M.-H. J. Org Chem.  1999,  64:  1331 
  • 5 Hayashi T. Kishi E. Soloshonok VA. Uozumi Y. Tetrahedron Lett.  1996,  37:  4969 
  • 6 Boger DL. Weinreb SM. Hetero Diels-Alder Methodology in Organic Synthesis, In Organic Chemistry   Vol. 47:  Wasserman HH. Academic Press; New York: 1987.  p.36 
  • 7 Boger DL. Corbett WL. Curran TT. Kasper AM.
    J. Am. Chem. Soc.  1991,  113:  1713 
  • 8 Jennings WB. Lovely CJ. Tetrahedron Lett.  1988,  29:  3725 
  • 9 Davis FA. Zhou P. Lal GS. Tetrahedron Lett.  1990,  31:  1653 
  • 10 Boger DL. Corbett WL. J. Org. Chem.  1992,  57:  4777 
  • 11 Ram RN. Khan AA. Synth. Commun.  2001,  31:  841 
  • 12 Garner SA. Krische MJ. J. Org. Chem.  2007,  72:  5843 
  • 13 Morimoto H. Lu G. Aoyama N. Matsunaga S. Shibasaki M. J. Am. Chem. Soc.  2007,  129:  9588 
  • 14 Xiao X. Wang H. Huang Z. Yang J. Bian X. Qin Y. Org. Lett.  2006,  8:  139 
  • 15 Chungh WJ. Omote M. Welch JT. J. Org. Chem.  2005,  70:  7784 
  • 16 Rassukana YV. Onys’ko PP. Davydova KO. Sinitsa AD. Tetrahedron Lett.  2004,  45:  3899 
  • 17 Shi M. Zhang W. Tetrahedron Asymmetry  2003,  14:  3407 
  • 18 Ma Z. Zhao Y. Jiang N. Jin X. Wang J. Tetrahedron Lett.  2002,  43:  3209 

Scheme 1