On the preparation of 2-substituted cephalosporins: Diels-Alder and 1,3-dipolar cycloadditions of 2-crotonoyl (=(2E)-but-2-enoyl), 2-sorboyl (=(2E,4E)-hexa-2,4-dienoyl), and 2-cinnamoyl (= (2E)-3-phenylprop-2-enoyl) substituted deacetoxycephalosporanate 1-oxides

László Tamás, Tamás E. Gunda, G. Batta, F. Sztaricskai

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Abstract

Cephalosporin sulfoxides 1 and 2 containing an enone- or dienone-type moiety at position 2 were treated with 2,3-dimethylbuta-1,3-diene or diethyl azodicarboxylate to synthesize, in Diels-Alder reactions, the new cephalosporin derivatives 4 and 5 with a cyclic substituent (Scheme 1). Under the same conditions, ethyl diazoacetate and diazomethane reacted differently: while reactions of 1 and 3 with the former lead to compounds 7-10 corresponding to the 1,3-dipolar cycloaddition route (Scheme 2), diazomethane produced only enol ethers 12 and 13, respectively (Scheme 3). This difference could be rationalized by assuming two different reaction pathways: an orbital-symmetry-controlled concerted cycloaddition and an ionic one.

Original languageEnglish
Pages (from-to)50-58
Number of pages9
JournalHelvetica Chimica Acta
Volume86
Issue number1
DOIs
Publication statusPublished - 2003

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Diazomethane
Cycloaddition
Cycloaddition Reaction
cycloaddition
Cephalosporins
Oxides
Sulfoxides
Diels-Alder reactions
preparation
Ethers
oxides
dienes
ethers
routes
Derivatives
orbitals
symmetry
diazoacetic ester

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "On the preparation of 2-substituted cephalosporins: Diels-Alder and 1,3-dipolar cycloadditions of 2-crotonoyl (=(2E)-but-2-enoyl), 2-sorboyl (=(2E,4E)-hexa-2,4-dienoyl), and 2-cinnamoyl (= (2E)-3-phenylprop-2-enoyl) substituted deacetoxycephalosporanate 1-oxides",
abstract = "Cephalosporin sulfoxides 1 and 2 containing an enone- or dienone-type moiety at position 2 were treated with 2,3-dimethylbuta-1,3-diene or diethyl azodicarboxylate to synthesize, in Diels-Alder reactions, the new cephalosporin derivatives 4 and 5 with a cyclic substituent (Scheme 1). Under the same conditions, ethyl diazoacetate and diazomethane reacted differently: while reactions of 1 and 3 with the former lead to compounds 7-10 corresponding to the 1,3-dipolar cycloaddition route (Scheme 2), diazomethane produced only enol ethers 12 and 13, respectively (Scheme 3). This difference could be rationalized by assuming two different reaction pathways: an orbital-symmetry-controlled concerted cycloaddition and an ionic one.",
author = "L{\'a}szl{\'o} Tam{\'a}s and Gunda, {Tam{\'a}s E.} and G. Batta and F. Sztaricskai",
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pages = "50--58",
journal = "Helvetica Chimica Acta",
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TY - JOUR

T1 - On the preparation of 2-substituted cephalosporins

T2 - Diels-Alder and 1,3-dipolar cycloadditions of 2-crotonoyl (=(2E)-but-2-enoyl), 2-sorboyl (=(2E,4E)-hexa-2,4-dienoyl), and 2-cinnamoyl (= (2E)-3-phenylprop-2-enoyl) substituted deacetoxycephalosporanate 1-oxides

AU - Tamás, László

AU - Gunda, Tamás E.

AU - Batta, G.

AU - Sztaricskai, F.

PY - 2003

Y1 - 2003

N2 - Cephalosporin sulfoxides 1 and 2 containing an enone- or dienone-type moiety at position 2 were treated with 2,3-dimethylbuta-1,3-diene or diethyl azodicarboxylate to synthesize, in Diels-Alder reactions, the new cephalosporin derivatives 4 and 5 with a cyclic substituent (Scheme 1). Under the same conditions, ethyl diazoacetate and diazomethane reacted differently: while reactions of 1 and 3 with the former lead to compounds 7-10 corresponding to the 1,3-dipolar cycloaddition route (Scheme 2), diazomethane produced only enol ethers 12 and 13, respectively (Scheme 3). This difference could be rationalized by assuming two different reaction pathways: an orbital-symmetry-controlled concerted cycloaddition and an ionic one.

AB - Cephalosporin sulfoxides 1 and 2 containing an enone- or dienone-type moiety at position 2 were treated with 2,3-dimethylbuta-1,3-diene or diethyl azodicarboxylate to synthesize, in Diels-Alder reactions, the new cephalosporin derivatives 4 and 5 with a cyclic substituent (Scheme 1). Under the same conditions, ethyl diazoacetate and diazomethane reacted differently: while reactions of 1 and 3 with the former lead to compounds 7-10 corresponding to the 1,3-dipolar cycloaddition route (Scheme 2), diazomethane produced only enol ethers 12 and 13, respectively (Scheme 3). This difference could be rationalized by assuming two different reaction pathways: an orbital-symmetry-controlled concerted cycloaddition and an ionic one.

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