PDF herunterladen
Synthesis 2003(12): 1895-1902
DOI: 10.1055/s-2003-41000
PAPER
© Georg ThiemeVerlag Stuttgart · New York

Novel Pyridine-Catalyzed Reactionof Dimethyl Acetylenedicarboxylate with Aldehydes and N-Tosylimines: Efficient Synthesis of2-Benzoylfumarates and 1-Azadienes

Vijay Nair*a, A. R. Sreekantha, N. Abhilasha, A. T. Bijua, B. Rema Devia, Rajeev. S. Menona, Nigam P. Rathb, R. Srinivasc
a Organic Chemistry Division, Regional Research Laboratory (CSIR), Trivandrum695 019, India
Fax: +91(472)2491712; e-Mail: vijaynair_2001@yahoo.com;
b Department of Chemistry, Universityof Missouri-St. Louis, Missouri-63121-4499, USA
c National Center for Mass Spectrometry, Indian Institute of Chemical Technology (CSIR), Hyderabad 500 007, India
Weitere Informationen

Publikationsverlauf

Received 4 November 2002
Publikationsdatum:
07. August 2003 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

A novel reaction of 1,4-dipolar intermediate 3,generated from pyridine and dimethyl acetylenedicarboxylate, witharomatic aldehydes, resulted in the facile synthesis of 2-benzoylfumaratesvia the elimination of pyridine, whereas with N-tosyliminesas dipolarophiles the reaction afforded highly substituted 1-azadienes.The reaction of pyridine and dimethyl acetylenedicarboxylate withN-substituted isatins, resulted in a novel three component condensation,affording spiropyrido[2,1-b][1,3]oxazinoderivatives in high yields via 1,4-dipolar cycloaddition.

Key words

aldehyde - pyridine - nucleophilic additions - dimethyl acetylenedicarboxylate - 1,4-dipolar cycloadditions

    References

  • 1a Dickstein JI. Miller SI. In The Chemistry of FunctionalGroup. The Chemistry of Carbon-Carbon Triple Bond   Part2:  Patai S. Wiley; Chichester: 1978.  Chap. 19. p.813-955  
    Google Scholar
  • 1b Winterfeldt E. In Chemistry of Acetylenes   Viehe HG. Dekker; NewYork: 1969.  p.267 
    Google Scholar
  • 1c Winterfeldt E. Angew.Chem., Int. Ed. Engl.  1967,  6:  423 
    Google Scholar
  • 2a Acheson RM. Adv. Heterocycl.Chem.  1963,  1:  125 
    Google Scholar
  • 2b Acheson RM. Elmore NF. Adv.Heterocycl. Chem.  1978,  23:  263 
    Google Scholar
  • 3 Diels O. Alder K. Liebigs Ann. Chem.  1932,  498:  16 
    CrossrefGoogle Scholar
  • 4a Acheson RM. Plunkett AO. J. Chem. Soc., Perkin Trans. 1  1975,  438 
    Google Scholar
  • 4b Acheson RM. Taylor GA. Proc. Chem.Soc.  1959,  186 
    Google Scholar
  • 4c Acheson RM. Taylor GA. J. Chem.Soc.  1960,  1691 
    Google Scholar
  • 4d Acheson RM. Gagan JMF. Taylor GA. J. Chem. Soc.  1963,  1903 
    Google Scholar
  • 5 Winterfeldt E. Chem.Ber.  1965,  98:  3537 
    CrossrefGoogle Scholar
  • 6 Acheson RM. Plunkett AO. J. Chem. Soc.  1964,  2676 
    Google Scholar
  • 7 Huisgen R. Morikawa M. Herbig K. Brunn E. Chem. Ber.  1967,  100:  1094 
    CrossrefGoogle Scholar
  • 8a Nair V. Vinod AU. Chem.Commun.  2000,  1019 
    CrossrefGoogle Scholar
  • 8b Nair V. Vinod AU. Nair JS. Sreekanth AR. Rath NP. Tetrahedron Lett.  2000,  41:  6675 
    CrossrefGoogle Scholar
  • 8c Nair V. Vinod AU. Rajesh C. J.Org. Chem.  2001,  66:  442 
    CrossrefGoogle Scholar
  • 8d Nair V. Bindu S. Balagopal L. TetrahedronLett.  2001,  42:  2043 
    CrossrefGoogle Scholar
  • 9 Nair V. Sreekanth AR. Vinod AU. Org.Lett.  2001,  3:  3495 
    CrossrefGoogle Scholar
  • 10 Nair V. Sreekanth AR. Vinod AU. Org. Lett.  2002,  4:  2807 
    CrossrefGoogle Scholar
  • For example, see:
  • 12a inventors; ; Jpn. Kokai  5838302. Nippon Synthetic ChemicalIndustry ; Chem. Abstr. 1983, 99, 1818
    Google Scholar
  • 12b inventors; , Jpn. Kokai  81127302. Nippon Synthetic ChemicalIndustry ; Chem. Abstr. 1982, 96, 2180
    Google Scholar
  • 13 Yamada K, Ino K, Takahashi S, Ohashi T, and Watanabe K. inventors; EuropeanPat. Appl. EP  239062.  ; Chem. Abstr. 1988, 109, 110904
  • 14a Chosakon Y, and Yamamoto N. inventors; Jpn.Kokai  63104940.  ; Chem. Abstr. 1988, 109, 230551
  • 14b Ikeda T, Hirano H, and Aoki K. inventors; Jpn.Kokai  63130564.  ; Chem. Abstr. 1989, 110, 7866
  • 14c Takahashi S, Ueda Y, Yanagida Y, Namito Y, Ohaska T, and Watanabe K. inventors; EuropeanPatent Appl. EP  204286.  ; Chem. Abstr. 1987, 106, 84179
  • 15a Iesce MR. Cermola F. Piazza A. Graziano ML. Scarpati R. Synthesis  1995,  439 
    Artikel in Thieme ConnectGoogle Scholar
  • 15b Iesce MR. Cermola F. Graziano ML. Scarpati R. Synthesis  1994,  944 
    Artikel in Thieme ConnectGoogle Scholar
  • 16 Winterfeldt E. Dillinger HJ. Chem. Ber.  1966,  99:  1558 
    CrossrefGoogle Scholar
  • 19a Schmidt U. Lieberknecht A. Wild J. Synthesis  1988,  159 
    CrossrefGoogle Scholar
  • 19b Trost BM. Dake GR. J.Am. Chem. Soc.  1997,  119:  7595 
    CrossrefGoogle Scholar
  • 20 HeteroDiels-Alder Methodology in Organic Synthesis   Boger DL. Weinreb SM. Academic Press; San Diego: 1987. 
    Google Scholar
  • 21a Juaristi E. EnantioselectiveSynthesis of β-Amino Acids   Wiley-VCH; NewYork: 1997. 
    CrossrefGoogle Scholar
  • 21b Gellman SH. Acc. Chem. Res.  1998,  31:  173 
    CrossrefGoogle Scholar
  • 22 Proctor GR. McKay WR. J. Chem. Soc., PerkinTrans. 1  1981,  2435 
    Google Scholar
11

Crystal Datafor 6: C40H32O2,M 293.23, Monoclinic, space group P21/c, unitcell dimensions a = 12.4082(9) Å, α = 90°; b = 12.1843(9) Å, β = 91.974(5)°, c = 8.6733(6) Å, γ = 90°, Rindices (all data) R1 = 0.1341, wR2 = 0.1335,volume, Z = 1310.50(16) Å3,4, Dcalc = 1.486 Mg/m3,absorption coefficient = 0.123 mm-1, λ = 0.71073 Å,reflections collected 22288.

17

Crystal datafor 26: C26H22N2O6,M 458.46, Monoclinic, space group = P21/n,unit cell diamensions a = 11.2763(2) Å, α = 90°, b = 9.28570(10) Å, β = 99.1180(10)°, c = 20.7237(3) Å, g = 90°,R indices (all data) R1 = 0.1003, wR2 = 0.1131,volume, Z = 2142.52(5) Å3,4, Dcalc = 1.421 Mg/m3,absorption coefficient = 0.102 mm-1, λ = 0.71073 Å,reflections collected = 56111.

18

Crystal datafor 30: C20H19NO6 S,M 401.42, Triclinic, space group P-1, unit cell diamensions a = 7.9631(3) Å, α = 83.827(2)°, b = 9.7212(3) Å, β = 74.064(2)°, c = 12.8578(4) Å, λ = 83.132(2)°,R indices (all data) R1 = 0.0643, wR2 = 0.1155,volume, Z = 947.30(5) Å3, 2, Dcalc = 1.407Mg/m 3, absorption coefficient = 0.209mm-1, λ = 0.71073 Å,reflections collected 14301.