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A solvolytic C-C cleavage reaction of 6-acetoxycyclohexa-2,4-dienones: Mechanistic implications for the intradiol catechol dioxygenases
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UNSPECIFIED (2001) A solvolytic C-C cleavage reaction of 6-acetoxycyclohexa-2,4-dienones: Mechanistic implications for the intradiol catechol dioxygenases. JOURNAL OF ORGANIC CHEMISTRY, 66 (6). pp. 2091-2097. ISSN 0022-3263.
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Abstract
6-Acetoxycyclohexa-2,4-dienones are found to undergo a rapid reaction in methanol/water under mildly basic conditions to give an acyclic ketoester as the major product for 6-phenyl and 6-methyl substrates. Reaction monitoring by UV spectroscopy indicates the formation of an unsaturated ketone reaction intermediate (lambda (max) 275 nm, R = Ph) and the transient appearance of a highly conjugated species. Reaction of the 6-phenyl substrate (4.95 x 10(-6) s(-1)) is 2-fold faster than the 6-methyl substrate (2.47 x 10(-6) s(-1)). The reaction rate is first order with respect to substrate concentration, and the final step in the reaction is ps-dependent. No cleavage was observed for a substrate lacking an acetyl substituent. A reaction mechanism for C-C cleavage is proposed involving a benzene oxide-oxepin interconversion. The possible relevance to the catalytic mechanism of the intradiol catechol dioxygenases is discussed.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Journal or Publication Title: | JOURNAL OF ORGANIC CHEMISTRY | ||||
Publisher: | AMER CHEMICAL SOC | ||||
ISSN: | 0022-3263 | ||||
Official Date: | 23 March 2001 | ||||
Dates: |
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Volume: | 66 | ||||
Number: | 6 | ||||
Number of Pages: | 7 | ||||
Page Range: | pp. 2091-2097 | ||||
Publication Status: | Published |
Data sourced from Thomson Reuters' Web of Knowledge
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