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DOI: 10.1055/s-2007-980341
Investigations of the [2,3]-Sigmatropic Rearrangements of Vinylaziridines and Allylic Amines
Publication History
Publication Date:
08 May 2007 (online)
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Abstract
This account summarizes our studies of [2,3]-sigmatropic rearrangements of vinylaziridines and allylic amines. The scope and limitations of the reactions as well as our present mechanistic understanding are also discussed.
1 Introduction
2 Aza-[2,3]-Wittig Rearrangement of Vinylaziridines
2.1 Early Attempts
2.2 Synthesis of Vinylaziridines
2.3 Rearrangement of Vinylaziridines
2.4 Total Synthesis of Indolizidines (-)-209B and (-)-209D
3 [2,3]-Sigmatropic Rearrangement of Allylic Amines
3.1 Lewis Acid Mediated Rearrangements
3.2 Asymmetric Rearrangements
4 Conclusions
Key words
rearrangements - vinylaziridines - ylides - pericyclic reactions - asymmetric reactions
- 1
Nakai K.Mikami K. Org. React. 1994, 46: 105 - 2
Marshall JA. In Comprehensive Organic Synthesis Vol. 3:Trost BM.Fleming I. Pergamon; Oxford: 1991. p.975-1014 - 3
Mikami K.Nakai T. Synthesis 1991, 594 - 4
Vogel C. Synthesis 1997, 497 - 5
Reetz MT.Schinzer D. Tetrahedron Lett. 1975, 16: 3485 - 6
Durst T.Elzen RVD.LeBelle MJ. J. Am. Chem. Soc. 1972, 94: 9261 - 7
Díez-Martin D.Kotecha NR.Ley SV.Mantegani S.Menéndez JC.Organ HM.White AD.Banks JB. Tetrahedron 1992, 48: 7899 - 8
Behrens CH.Sharpless KB. J. Org. Chem. 1985, 50: 5696 - 9
Ittah Y.Sasson Y.Shahak I.Tsaroom S.Blum J. J. Org. Chem. 1978, 43: 4271 - 10
Åhman J.Jarevång T.Somfai P. J. Org. Chem. 1996, 61: 8148 - 11
Åhman J.Somfai P.Tanner D. J. Chem. Soc., Chem. Commun. 1994, 2785 - 12
Åhman J.Somfai P. Tetrahedron 1999, 55: 11595 - 13
Hussenius A.Somfai P.Tanner D. J. Phys. Org. Chem. 1996, 9: 623 -
14a
Olofsson B.Somfai P. J. Org. Chem. 2002, 67: 8574 -
14b
Lindström UM.Somfai P. Synthesis 1998, 109 - 15
Burke CP.Shi Y. Angew. Chem. Int. Ed. 2006, 45: 4475 - 16
Barrett AGM.Seefeld MA.White AJP. J. Org. Chem. 1996, 61: 2677 - 17
Åhman J.Somfai P. J. Am. Chem. Soc. 1994, 116: 9781 - 18
Åhman J.Somfai P. Tetrahedron Lett. 1996, 37: 2495 - 19
Wu Y.-D.Houk KN.Marshall JA. J. Org. Chem. 1990, 55: 1421 - 22
Åhman J.Somfai P. Tetrahedron Lett. 1995, 36: 303 - 23
Åhman J.Somfai P. Tetrahedron 1995, 51: 9747 - 24
Daly JW.Spande TF. In Alkaloids: Chemical and Biological Perspectives Vol. 5:Pelletier SW. Wiley; New York: 1986. Chap. 1. - 25
Moffett MW. National Geographic 1995, 187: 98 - 26
Aronstam RS.Daly JW.Spande TF.Narayanan TK.Albuquerque EX. Neurochem. Res. 1986, 11: 1227 - 27
Anderson JC.Siddons DC.Smith SC.Swarbrick ME. J. Chem. Soc., Chem. Commun. 1995, 1835 - 28
Murata Y.Nakai T. Chem. Lett. 1990, 2069 - 29
Kessar SV.Singh P.Singh KN.Kaul VK.Kumar G. Tetrahedron Lett. 1995, 36: 8481 . In our hands it has not been possible to repeat the experiments described in this report - 30
Coldham I.Middleton ML.Taylor PL. J. Chem. Soc., Perkin Trans. 1 1998, 2817 -
31a
Blid J.Somfai P. Tetrahedron Lett. 2003, 44: 3159 -
31b
Blid J.Brandt P.Somfai P. J. Org. Chem. 2004, 69: 3043 - 33
Markó IE. In Comprehensive Organic Synthesis Vol. 3:Trost BM.Fleming I. Pergamon; Oxford: 1991. p.913-974 -
34a
Kaiser GV.Ashbrook CW.Baldwin JE. J. Am. Chem. Soc. 1971, 93: 2342 -
34b
Hiroi K.Nakazawa K. Chem. Lett. 1980, 1077 -
34c
Clark JS.Hodgson PB. Tetrahedron Lett. 1995, 36: 2519 -
34d
Gawley RE.Zhang Q.Campagna S. J. Am. Chem. Soc. 1995, 117: 11817 -
34e
Glaeske KW.West FG. Org. Lett. 1999, 1: 31 -
34f
Aggarwal VK.Fang G.Charmant JPH.Meek G. Org. Lett. 2003, 5: 1757 -
34g For a general overview of the asymmetric [2,3]-Wittig rearrangement, see:
Nakai T.Tomooka K. Pure Appl. Chem. 1997, 69: 595 - 35
Workman JA.Garrido NP.Sançon J.Roberts E.Wessel HP.Sweeney JB. J. Am. Chem. Soc. 2005, 127: 1066 - 36
Fujimoto K.Matsuhashi C.Nakai T. Heterocycles 1996, 42: 423 -
37a
Cagle PC.Arif AM.Gladysz JA. J. Am. Chem. Soc. 1994, 116: 3655 -
37b
Meyer O.Cagle PC.Weickhardt K.Vichard D.Gladysz JA. Pure Appl. Chem. 1996, 68: 79 - 38
Corey EJ.Imwinkelried R.Pikul S.Xiang YB. J. Am. Chem. Soc. 1989, 111: 5493 - 39
Blid J.Panknin O.Somfai P. J. Am. Chem. Soc. 2005, 127: 9352 - 41 For a more detailed discussion of the asymmetric [2,3]-sigmatropic rearrangement, see:
Blid J.Panknin O.Tuzina P.Somfai P. J. Org. Chem. 2007, 72: 1294
References and Notes
Somfai P., unpublished results.
21Ottosson H., Somfai P., unpublished results.
32InCl3 and ZnCl2 gave low yields; other unsuccessful Lewis acids were CuCl, CuCl2, TiCl4, Yb(OTf)3, FeCl3, ZrCl2Cp2, and ScCl3.
40PhMe: 70% yield, er ≥ 98.5:1.5; Et2O: 27% yield,
er ≥ 98.5:1.5; THF: 15% yield, er = 92:8.