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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
Further Information

Publication History

Received 4 November 2002
Publication Date:
07 August 2003 (online)

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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

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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.