The first synthesis of cyclopropanone acetals from the reaction of Fischer carbene complexes with ketene acetals

Siu Ling B. Wang, Daniel R. Goldberg, Xuejun Liu, Jing Su, Qi Huang Zheng, Vincent Liptak, William D. Wulff

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

The reaction of iso-propoxy stabilized Fischer carbene complexes with ketene acetals gives moderate to excellent yields of cyclopropanone acetals when carried out under a carbon monoxide atmosphere. This is in contrast to the known reaction of methoxy substituted complexes which give cyclic ortho esters under the same conditions. A mechanism is proposed which involves a branch point between the two products as the zwitterionic intermediate resulting from nucleophilic addition of the ketene acetal to the carbene carbon. A 1,3-migration of the methoxyl group to the cationic center leads to the ortho ester and a ring closure by backside attack leads to the cyclopropanone acetal. A double-labeling experiment shows that the 1,3-migration occurs by an intramolecular process that is proposed to involve a bridging oxonium ion. The effect of the isopropoxy group is thus interpreted to be to sterically hinder the formation of a bridged oxonium ion.

Original languageEnglish (US)
Pages (from-to)6101-6110
Number of pages10
JournalJournal of Organometallic Chemistry
Volume690
Issue number24-25
DOIs
StatePublished - Dec 1 2005
Externally publishedYes

Keywords

  • Cross-over experiment
  • Cyclopropanone acetals
  • Fischer carbene complexes
  • Ketene acetals
  • Zwitterionic intermediate

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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