Transformation of penicillins into 3-substituted Δ3-cephems through addition/cyclization of allenecarboxylates

Hideo Tanaka, Shin Ichi Sumida, Yutaka Kameyama, Koichi Sorajo, Isao Wada, Sigeru Torii

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

A straightforward synthesis of Δ3-cephems 2 bearing heteroatom substituents directly attached to C(3)-position was performed successfully by a sequential addition/cyclization reaction of allenecarboxylate 4 derived from eithen penicillin 1. Upon treatment of the allenecarboxylate 4 with morpholine, pyrrolidine, sodium azide, and 5-methyl-1,3,4-thiadiazole-2-thiol in DMF in the presence of calcium chloride, the addition/cyclization reaction proceeded smoothly to afford the corresponding 3-substituted Δ3-cephems 2a-e. Reaction of the allenecarboxylate 4 with lithium chloride in NMP (N-methyl-2-pyrrolidone) in the presence of aluminum chloride afforded 3-chloro-Δ3-cephem 2f, while without aluminum chloride, 3-phenylsulfonyl-Δ3-cephem 2e was mainly obtained. The 3-sulfenyl-Δ3-cephems 12 were prepared by a similar addition/cyclization reaction of allenecarboxylates 10 with a catalytic amount of thiolates. The sulfenyl moieties attached at the sulfur atom of the C(4)-substituent of 10 were introduced at the C(3)-position of the cephem framework 2.

Original languageEnglish
Pages (from-to)3651-3658
Number of pages8
JournalBulletin of the Chemical Society of Japan
Volume69
Issue number12
DOIs
Publication statusPublished - Dec 1 1996

ASJC Scopus subject areas

  • Chemistry(all)

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