Synthesis of 2-exo-methylenepenam and 3-chloro-Δ3-cephem through a sequential reductive 1,2-elimination/S-S bond fission or chloride ion-addition/cyclization of 3,4-disubstituted 2-butenoates in metal salt/metal combinations

H. Tanaka, S. Sumida, Y. Nishioka, N. Kobayashi, Y. Tokumaru, Y. Kameyama, S. Torii

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Abstract

Synthesis of 2-exo-methylenepenam 1 through a sequential reductive 1,2-elimination/S-S bond fission/cyclization of 6 was performed by treatment with a PbBr2/Al (or a BiCl3/Al) combination in DMF, while that of 3-chloro-Δ3-cephem 2 through reductive 1,2-elimination/chloride ion-addition/cyclization was attained by use of an AlCl3/Al combination in N-methylpyrrolidone (NMP). The selective transformation of 6 to the allenecarboxylate 3 was also achieved by treatment with an AlBr3/Al combination in NMP. Cyclic voltammograms of 3,4-disubstituted 2-[2-oxo-3-(phenylacetamido)-4-[(phenylsulfonyl)thio]azetidin-1-yl]-2- butenoates (6) exhibit two irreversible reduction peaks responsible for reductive 1,2-elimination of the 3,4-disubstituted 2-butenoate moiety (at less negative potential) and for reductive S-S bond fission of the (phenylsulfonyl)thio moiety, suggesting that the reductive 1,2-elimination of 6 leading to allenecarboxylate 3 would occur prior to the reductive S-S bond cleavage.

Original languageEnglish
Pages (from-to)3610-3617
Number of pages8
JournalJournal of Organic Chemistry
Volume62
Issue number11
DOIs
Publication statusPublished - 1997

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Cyclization
Chlorides
Salts
Metals
Ions
N-methylpyrrolidone
aluminum chloride
3'-dimethylaminoflavone

ASJC Scopus subject areas

  • Organic Chemistry

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Synthesis of 2-exo-methylenepenam and 3-chloro-Δ3-cephem through a sequential reductive 1,2-elimination/S-S bond fission or chloride ion-addition/cyclization of 3,4-disubstituted 2-butenoates in metal salt/metal combinations. / Tanaka, H.; Sumida, S.; Nishioka, Y.; Kobayashi, N.; Tokumaru, Y.; Kameyama, Y.; Torii, S.

In: Journal of Organic Chemistry, Vol. 62, No. 11, 1997, p. 3610-3617.

Research output: Contribution to journalArticle

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abstract = "Synthesis of 2-exo-methylenepenam 1 through a sequential reductive 1,2-elimination/S-S bond fission/cyclization of 6 was performed by treatment with a PbBr2/Al (or a BiCl3/Al) combination in DMF, while that of 3-chloro-Δ3-cephem 2 through reductive 1,2-elimination/chloride ion-addition/cyclization was attained by use of an AlCl3/Al combination in N-methylpyrrolidone (NMP). The selective transformation of 6 to the allenecarboxylate 3 was also achieved by treatment with an AlBr3/Al combination in NMP. Cyclic voltammograms of 3,4-disubstituted 2-[2-oxo-3-(phenylacetamido)-4-[(phenylsulfonyl)thio]azetidin-1-yl]-2- butenoates (6) exhibit two irreversible reduction peaks responsible for reductive 1,2-elimination of the 3,4-disubstituted 2-butenoate moiety (at less negative potential) and for reductive S-S bond fission of the (phenylsulfonyl)thio moiety, suggesting that the reductive 1,2-elimination of 6 leading to allenecarboxylate 3 would occur prior to the reductive S-S bond cleavage.",
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AU - Tanaka, H.

AU - Sumida, S.

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AU - Tokumaru, Y.

AU - Kameyama, Y.

AU - Torii, S.

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AB - Synthesis of 2-exo-methylenepenam 1 through a sequential reductive 1,2-elimination/S-S bond fission/cyclization of 6 was performed by treatment with a PbBr2/Al (or a BiCl3/Al) combination in DMF, while that of 3-chloro-Δ3-cephem 2 through reductive 1,2-elimination/chloride ion-addition/cyclization was attained by use of an AlCl3/Al combination in N-methylpyrrolidone (NMP). The selective transformation of 6 to the allenecarboxylate 3 was also achieved by treatment with an AlBr3/Al combination in NMP. Cyclic voltammograms of 3,4-disubstituted 2-[2-oxo-3-(phenylacetamido)-4-[(phenylsulfonyl)thio]azetidin-1-yl]-2- butenoates (6) exhibit two irreversible reduction peaks responsible for reductive 1,2-elimination of the 3,4-disubstituted 2-butenoate moiety (at less negative potential) and for reductive S-S bond fission of the (phenylsulfonyl)thio moiety, suggesting that the reductive 1,2-elimination of 6 leading to allenecarboxylate 3 would occur prior to the reductive S-S bond cleavage.

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