Facile access to 3-allyl- and 3-benzyl-Δ3-cephems through reductive addition/cyclization of allenecarboxylate with allylic and benzylic halides in an [NiCl2(bipy)]/PbBr2/Al redox system

Hideo Tanaka, Shin Ichi Sumida, Kouichi Sorajo, Yutaka Kameyama, Sigeru Torii

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Sequential reductive addition/cyclization of the allenecarboxylate 1, derived from penicillin G, with allylic and benzylic halides is successfully achieved by the aid of a three-metal redox system consisting of aluminium metal (2.5 molar equiv.) and catalytic amounts of [NiCl2(bipy)] (0.1 molar equiv.) and PbBr2 (0.05 molar equiv.) in N-methyl-l-pyrrolidone (NMP) to afford the corresponding 3-allyl- and 3-benzyl-Δ3-cephems 3a-i in 20-85% yields. The reactions of 1 with vinyl, prop-2-ynyl and phenyl halides in the same three-metal redox system result in the recovery of 1 and/or partial formation of 2-exo-methylenepenam 4. A similar electroreductive addition/cyclization of 1 with allyl bromide is performed by passage of an electrical current (3.2 F mol-1) in an [NiCl2(bipy)]/PbBr2/NMP/(Pt cathode)-(Al anode) system.

Original languageEnglish
Pages (from-to)637-642
Number of pages6
JournalJournal of the Chemical Society, Perkin Transactions 1
Issue number5
Publication statusPublished - Mar 7 1997

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Cyclization
Pyrrolidinones
Metals
Penicillin G
Aluminum
Anodes
Cathodes
Recovery
Oxidation-Reduction

ASJC Scopus subject areas

  • Organic Chemistry

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Facile access to 3-allyl- and 3-benzyl-Δ3-cephems through reductive addition/cyclization of allenecarboxylate with allylic and benzylic halides in an [NiCl2(bipy)]/PbBr2/Al redox system. / Tanaka, Hideo; Sumida, Shin Ichi; Sorajo, Kouichi; Kameyama, Yutaka; Torii, Sigeru.

In: Journal of the Chemical Society, Perkin Transactions 1, No. 5, 07.03.1997, p. 637-642.

Research output: Contribution to journalArticle

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