Synthesis 2012; 44(18): 2863-2871
DOI: 10.1055/s-0031-1291137
special topic
© Georg Thieme Verlag Stuttgart · New York

d-Allal- and d-Galactal-Derived Vinyl N-Mesylaziridines: Regio- and Stereoselectivity in Addition Reactions of O-, C-, N-, and S-Nucleophiles

Valeria Di Bussolo*
Dipartimento di Scienze Farmaceutiche, sede Chimica Bioorganica e Biofarmacia, Università di Pisa, Via Bonanno 33, 56126 Pisa, Italy, Fax: +39(050)2219660   Email: paolo.crotti@farm.unipi.it
,
Ileana Frau
Dipartimento di Scienze Farmaceutiche, sede Chimica Bioorganica e Biofarmacia, Università di Pisa, Via Bonanno 33, 56126 Pisa, Italy, Fax: +39(050)2219660   Email: paolo.crotti@farm.unipi.it
,
Mauro Pineschi
Dipartimento di Scienze Farmaceutiche, sede Chimica Bioorganica e Biofarmacia, Università di Pisa, Via Bonanno 33, 56126 Pisa, Italy, Fax: +39(050)2219660   Email: paolo.crotti@farm.unipi.it
,
Paolo Crotti*
Dipartimento di Scienze Farmaceutiche, sede Chimica Bioorganica e Biofarmacia, Università di Pisa, Via Bonanno 33, 56126 Pisa, Italy, Fax: +39(050)2219660   Email: paolo.crotti@farm.unipi.it
› Author Affiliations
Further Information

Publication History

Received: 27 February 2012

Accepted after revision: 15 March 2012

Publication Date:
14 June 2012 (eFirst)

Abstract

The regioselectivity and stereoselectivity were examined of the addition reactions of O-, C-, N- and S-nucleophiles to d-allal- and d-galactal-derived N-mesylaziridines. The ratio of 1,4-regioselectivity (exclusive syn-1,4-addition) to 1,2-regioselectivity (exclusive anti-1,2-addition) was strictly and directly dependent on the ability of the nucleophile to coordinate with the nitrogen atom of the aziridine.

 
  • References

    • 1a van den Bos LJ, Codée JD. C, van Boom JH, Overkleeft HS, van der Marel GA. Org. Biomol. Chem. 2003; 1: 4160
    • 1b Bernfield M, Gotte M, Park PW, Reizes O, Fitzgerald ML, Lincecum J, Zako M. Annu. Rev. Biochem. 1999; 68: 729
    • 1c Dwek RA. Chem. Rev. 1996; 96: 683
    • 1d Banoub J, Boullanger P, Lafont D. Chem. Rev. 1992; 92: 1167
    • 2a Choi Y.-H, Roehrl MH, Kasper DL, Wang JY. Biochemistry 2002; 41: 15144
    • 2b Kotra LP, Mobashery S. Curr. Org. Chem. 2001; 5: 193
    • 2c Wang Y, Kalka-Moll WM, Roehrl MH, Kasper DL. Proc. Natl. Acad. Sci. U.S.A. 2000; 97: 13478
    • 2d Sears P, Wong C.-H. Angew. Chem. Int. Ed. 1999; 38: 2301
  • 3 Knapp S. Chem. Soc. Rev. 1999; 28: 61
    • 4a Di Bussolo V, Romano MR, Pineschi M, Crotti P. Org. Lett. 2005; 7: 1299
    • 4b Di Bussolo V, Favero L, Romano MR, Pineschi M, Crotti P. J. Org. Chem. 2006; 71: 1696
    • 4c Di Bussolo V, Romano MR, Pineschi M, Crotti P. Tetrahedron 2007; 63: 2482
  • 5 Reaction conditions: Protocol A: the nucleophile is also the solvent for the reaction. Protocol B: only 3–4 equiv of the nucleophile are present in MeCN or benzene as the solvent. The complete 1,4-regioselectivity and directly substrate-dependent; stereoselectivity found in the glycosylation of alcohols by aziridines and was always observed under Protocol B conditions and, in the case of t-BuOH, also under Protocol A conditions; see also ref. 4
  • 6 In this framework, anti-1,2- and anti-1,4-addition products, which are assumed to derive from attack of a free noncoordinated nucleophile, are simply named noncoordination products. The coordination and noncoordination product nomenclature is used throughout the text for appropriate modes of formation
  • 7 Di Bussolo V, Checchia L, Romano MR, Favero L, Pineschi M, Crotti P. Tetrahedron 2010; 66: 689
  • 8 Because of their instability and reactivity, the preparation of aziridines and by base-catalyzed cyclization reactions of the corresponding precursors and , respectively, has to be carried out in the presence of the selected nucleophile
    • 9a Di Bussolo V, Caselli M, Romano MR, Pineschi M, Crotti P. J. Org. Chem. 2004; 69: 7383
    • 9b Di Bussolo V, Caselli M, Romano MR, Pineschi M, Crotti P. J. Org. Chem. 2004; 69: 8702
  • 10 Bonner OD. J. Phys. Chem. 1979; 83: 1218
  • 11 Di Bussolo V, Favero L, Romano MR, Pineschi M, Crotti P. Tetrahedron 2008; 64: 8188
  • 12 Di Bussolo V, Caselli M, Pineschi M, Crotti P. Org. Lett. 2003; 5: 2173
  • 13 Jamie C, Ortuño RM, Font J. J. Org. Chem. 1988; 53: 139
  • 14 Chini M, Crotti P, Flippin LA, Macchia F. Tetrahedron Lett. 1989; 30: 6563
  • 15 Papa AJ. J. Org. Chem. 1966; 31: 1426
  • 16 Moss RA, Terpinski J, Cox DP, Denney DZ, Krogh-Jespersen K. J. Am. Chem. Soc. 1985; 107: 2743