Highly Regioselective and Efficient
Synthesis of Aminoepoxides by Ring Closure of Aminohalohydrins
Mediated by KF-Celite

Vittorio Pace; Pilar Hoyos; José Vicente Sinisterra; Andrés R. Alcántara; Wolfgang Holzer

doi:10.1055/s-0030-1260961

LETTER

Highly Regioselective and Efficient Synthesis of Aminoepoxides by Ring Closure of Aminohalohydrins Mediated by KF-Celite

Vittorio Pace*^a,b, Pilar Hoyos^b, José Vicente Sinisterra^b,c, Andrés R. Alcántara^b, Wolfgang Holzer^a
^a Department of Drug and Natural Product Synthesis, Faculty of Life Sciences, University of Vienna, Althanstr. 14, 1090 Vienna, Austria
^b Biotransformations Group, Organic and Pharmaceutical Chemistry Department, Complutense University of Madrid, Plaza Ramón y Cajal s/n, 28040 Madrid, Spain
Fax: +34(913)941822; e-Mail: vpace@farm.ucm.es;
^c Industrial Biotransformations Unit, Scientific Park of Madrid, 28760 Tres Cantos, Madrid, Spain

Abstract

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Abstract

The regioselective synthesis of several aminoepoxides has been achieved without observing any trace of azetidinols, which are usually reported as the exclusive reaction products when aminohalohydrins are treated with bases. The use of the mild supported base KF-Celite in refluxing acetonitrile is crucial for modulating the excellent regioselectivity observed.

Key words

epoxides - amino alcohols - regioselectivity - ring closure - epoxidation

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References

1 Aziridines and Epoxides in Organic Synthesis Yudin AK. Wiley-VCH; Weinheim: 2006.

2 Hodgson DM. Humphreys PG. Hughes SP. Pure Appl. Chem. 2007, 79: 269

3 Sello G. Fumagalli T. Orsini F. Curr. Org. Synth. 2006, 3: 457

4 Wong OA. Shi Y. Chem. Rev. 2008, 108: 3958

5 Yang D. Acc. Chem. Res. 2004, 37: 497

6 Aggarwal VK. Winn CL. Acc. Chem. Res. 2004, 37: 611

7 Fringuelli F. Piermatti O. Pizzo F. Vaccaro L. J. Org. Chem. 1999, 64: 6094

8 Shivani BP. Pujala B. Chakraborti AK. J. Org. Chem. 2007, 72: 3713

9 Elenkov MM. Hauer B. Janssen DB. Adv. Synth. Catal. 2006, 348: 579

10 Lutje Spelberg JH. Tang L. van Gelder M. Kellogg RM. Janssen DB. Tetrahedron: Asymmetry 2002, 13: 1083

11 Stamatov SD. Stawinski J. Tetrahedron Lett. 2006, 47: 2543

12 Constable DJC. Curzons AD. Cunningham VL. Green Chem. 2002, 4: 521

13 Izawa K. Onishi T. Chem. Rev. 2006, 106: 2811

14 Cunico W. Gomes CRB. Moreth M. Manhanini DP. Figueiredo IH. Penido C. Henriques MGMO. Varotti FP. Krettli AU. Eur. J. Med. Chem. 2009, 44: 1363

15 Charrier N. Clarke B. Cutler L. Demont E. Dingwall C. Dunsdon R. East P. Hawkins J. Howes C. Hussain I. Jeffrey P. Maile G. Matico R. Mosley J. Naylor A. O’Brien A. Redshaw S. Rowland P. Soleil V. Smith KJ. Sweitzer S. Theobald P. Vesey D. Walter DS. Wayne G. J. Med. Chem. 2008, 51: 3313

16 Badarau E. Suzenet F. Bojarski AJ. Fînaru A.-L. Guillaumet G. Bioorg. Med. Chem. Lett. 2009, 19: 1600

17 Pace V. Verniest G. Sinisterra JV. Alcántara AR. De Kimpe N. J. Org. Chem. 2010, 75: 5760

18 Barluenga J. Baragana B. Concellon JM. J. Org. Chem. 1995, 60: 6696

19 Pace V. Martínez F. Fernández M. Sinisterra JV. Alcántara AR. Adv. Synth. Catal. 2009, 351: 3199

20 Pace V. Cortés-Cabrera A. Fernández M. Sinisterra JV. Alcántara AR. Synthesis 2010, 3545

21 Proctor LD. Warr AJ. Org. Proc. Res. Dev. 2002, 6: 884

22 Perrault WR. Pearlman BA. Godrej DB. Jeganathan A. Yamagata K. Chen JJ. Lu CV. Herrinton PM. Gadwood RC. Chan L. Lyster MA. Maloney MT. Moeslein JA. Greene ML. Barbachyn MR. Org. Proc. Res. Dev. 2003, 7: 533

23 Ngoc Tam NT. Magueur G. Ourévitch M. Crousse B. Bégué J.-P. Bonnet-Delpon DL. J. Org. Chem. 2005, 70: 699

24 Williams DBG. Cullen A. J. Org. Chem. 2009, 74: 9509

25 Chen P. Cheng PTW. Spergel SH. Zahler R. Wang X. Thottathil J. Barrish JC. Polniaszek RP. Tetrahedron Lett. 1997, 38: 3175

26 Reddy VVRMK. Udaykiran D. Chintamani US. Mahesh Reddy E. Kameswararao C. Madhusudhan G. Org. Proc. Res. Dev. 2011, 15: 462

27 Reddy VVRMK. Babu KK. Ganesh A. Srinivasulu P. Madhusudhan G. Mukkanti K. Org. Proc. Res. Dev. 2010, 14: 931

28 Brandi A. Cicchi S. Cordero FM. Chem. Rev. 2008, 108: 3988

29 Gaertner VR. J. Org. Chem. 1967, 32: 2972

30 Okutani T. Kaneko T. Masuda K. Chem. Pharm. Bull. 1974, 22: 1490

31 Ibuka T. Nakai K. Habashita H. Hotta Y. Otaka A. Tamamura H. Fujii N. Mimura N. Miwa Y. Chounan Y. Yamamoto Y. J. Org. Chem. 1995, 60: 2044

32 Oh HC. Rhim CY. You CH. Cho JR. Synth. Commun. 2003, 33: 4297

33 Karikomi M. Arai K. Toda T. Tetrahedron Lett. 1997, 38: 6059

34 Pace V. Sinisterra JV. Alcántara AR. Curr. Org. Chem. 2010, 14: 2384

35 Pace V. Martínez F. Fernández M. Sinisterra JV. Alcántara AR. Org. Lett. 2007, 9: 2661

36 Basu B. Das P. Das S. Curr. Org. Chem. 2008, 12: 141

37 Blass BE. Tetrahedron 2002, 58: 9301

38 Pace V. Martínez F. Nova CI. Fernández M. Sinisterra JV. Alcántara AR. Tetrahedron Lett. 2009, 50: 3050

39 Pace V. Hoyos P. Fernández M. Sinisterra JV. Alcántara AR. Green Chem. 2010, 12: 1380

40 Pace V. Castoldi L. Hoyos P. Sinisterra JV. Pregnolato M. Sánchez-Montero JM. Tetrahedron 2011, 67: 2670

41 Clark JH. Chem. Rev. 1980, 80: 429

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