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 journalArticle

7 Citations (Scopus)

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

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acetals
Acetals
carbenes
Esters
Ions
synthesis
Carbon monoxide
Labeling
esters
Carbon
Carbon Monoxide
Atmosphere
carbon monoxide
attack
closures
marking
ions
Experiments
atmospheres
carbene

Keywords

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

ASJC Scopus subject areas

  • Chemical Engineering (miscellaneous)
  • Materials Science (miscellaneous)
  • Materials Chemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Biochemistry

Cite this

The first synthesis of cyclopropanone acetals from the reaction of Fischer carbene complexes with ketene acetals. / Wang, Siu Ling B; Goldberg, Daniel R.; Liu, Xuejun; Su, Jing; Zheng, Qi-Huang; Liptak, Vincent; Wulff, William D.

In: Journal of Organometallic Chemistry, Vol. 690, No. 24-25, 01.12.2005, p. 6101-6110.

Research output: Contribution to journalArticle

Wang, Siu Ling B ; Goldberg, Daniel R. ; Liu, Xuejun ; Su, Jing ; Zheng, Qi-Huang ; Liptak, Vincent ; Wulff, William D. / The first synthesis of cyclopropanone acetals from the reaction of Fischer carbene complexes with ketene acetals. In: Journal of Organometallic Chemistry. 2005 ; Vol. 690, No. 24-25. pp. 6101-6110.
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AU - Goldberg, Daniel R.

AU - Liu, Xuejun

AU - Su, Jing

AU - Zheng, Qi-Huang

AU - Liptak, Vincent

AU - Wulff, William D.

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AB - 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.

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