One-pot synthesis of five-membered cyclic thioethers or ethers via intramolecular nitrile oxide-olefin cycloaddition (INOC) or intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) by the use of methyl chloroformate

Ming Chung Yan, Jing Yuan Liu, Wen Wei Lin, Kuo Hsi Kao, Ju Tsung Liu, Jeong Jiunn Jang, Ching Fa Yao

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

Reaction of β-nitrostyrenes 1 with allyl mercaptan 2 in the presence of triethylamine generated unsaturated nitro sulfides 3 and then the solution was treated with methyl chloroformate (MCF) and was refluxed to obtain [3.3.0]bicyclic products trans-6 and cis-6 in one-pot. The ratios of trans- 6:cis-6 were from 1.1:1 to 1.8:1 and the mechanism of the formation 6 is proposed to proceed through the formation of nitrile oxides 5 to undergo intramolecular nitrile oxide-olefin cycloaddition (INOC). Nitronates 16, prepared from 1 with allyl alcohol and base, can be converted into methoxycarbonyl nitronates 22 by treating the solution with methyl chloroformate and catalytic amount of 4-dimethylaminopyridine (DMAP) in the presence of different amounts of triethylamine. Intermediates 22 can either undergo intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) to generate highly stereoselective product trans-14 or undergo INOC to yield trans-14 and cis-14. The application of this improved methodology to synthesize different heterocyclic products 10, 26, and 27 is reported.

Original languageEnglish
Pages (from-to)12493-12514
Number of pages22
JournalTetrahedron
Volume55
Issue number43
DOIs
Publication statusPublished - 1999 Oct 22

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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