Allylic Displacements and a Novel Ester-Ether Interchange in Fused Cyclobutanones

Alfred Hassner; John Dillon

doi:10.1021/jo00367a012

Allylic Displacements and a Novel Ester-Ether Interchange in Fused Cyclobutanones

Alfred Hassner, John Dillon

Research output: Contribution to journal › Article › peer-review

22 Scopus citations

Abstract

Chlorophenylcyclobutanone 11, prepared by chlorophenylketene addition to cyclohexene, reacts readily with simple and hindered carboxylic acids in a cine substitution to produce keto esters 14. The acyloxy and phenyl substituents in 14c are shown by X-ray diffraction to be cis oriented; nevertheless 14 reacts with NaOMe at 20 °C by an unusual ester-ether interchange to produce 15 and the released carboxylate RCO2^-. These reactions apparently proceed via an oxyallyl cation intermediate. The behaviors of related cyclobutanones 4, 6, and 11 with methoxide are contrasted.

Original language	English
Pages (from-to)	3315-3319
Number of pages	5
Journal	Journal of Organic Chemistry
Volume	51
Issue number	17
DOIs	https://doi.org/10.1021/jo00367a012
State	Published - 1986
Externally published	Yes

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abstract = "Chlorophenylcyclobutanone 11, prepared by chlorophenylketene addition to cyclohexene, reacts readily with simple and hindered carboxylic acids in a cine substitution to produce keto esters 14. The acyloxy and phenyl substituents in 14c are shown by X-ray diffraction to be cis oriented; nevertheless 14 reacts with NaOMe at 20 °C by an unusual ester-ether interchange to produce 15 and the released carboxylate RCO2-. These reactions apparently proceed via an oxyallyl cation intermediate. The behaviors of related cyclobutanones 4, 6, and 11 with methoxide are contrasted.",

author = "Alfred Hassner and John Dillon",

year = "1986",

doi = "10.1021/jo00367a012",

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AB - Chlorophenylcyclobutanone 11, prepared by chlorophenylketene addition to cyclohexene, reacts readily with simple and hindered carboxylic acids in a cine substitution to produce keto esters 14. The acyloxy and phenyl substituents in 14c are shown by X-ray diffraction to be cis oriented; nevertheless 14 reacts with NaOMe at 20 °C by an unusual ester-ether interchange to produce 15 and the released carboxylate RCO2-. These reactions apparently proceed via an oxyallyl cation intermediate. The behaviors of related cyclobutanones 4, 6, and 11 with methoxide are contrasted.

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Allylic Displacements and a Novel Ester-Ether Interchange in Fused Cyclobutanones

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