Intramolecular [2+2] Cycloadditions of Phenoxyketenes and Intermolecular [2+2] Cycloadditions of Aminoketenes

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One objective of this study was to explore the intramolecular [2+2] cycloadditions of phenoxyketenes to carbonyl groups with isoflavones and benzofurans as target compounds. The other objective was to investigate the eyeloaddition reactions of rarely studied aminoketenes. The conversion of 2-(carboxyalkoxy)benzils to the corresponding phenoxyketenes leads to an intramolecular [2+2] cycloaddition to ultimately yield isoflavones and/or 3-aroylbenzofurans. The product distributions are dependent upon the substitution pattern in the original benzil acids. The initial cycloaddition products, β-lactones, are isolated in some instances while some β-lactones spontaneously underwent decarboxylation and could not be isolated. The ketene intermediate was demonstrated in the intramolecular ... continued below

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iv, 116 leaves: ill.

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Gu, Yi Qi May 1989.

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  • Gu, Yi Qi

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One objective of this study was to explore the intramolecular [2+2] cycloadditions of phenoxyketenes to carbonyl groups with isoflavones and benzofurans as target compounds. The other objective was to investigate the eyeloaddition reactions of rarely studied aminoketenes.
The conversion of 2-(carboxyalkoxy)benzils to the corresponding phenoxyketenes leads to an intramolecular [2+2] cycloaddition to ultimately yield isoflavones and/or 3-aroylbenzofurans. The product distributions are dependent upon the substitution pattern in the original benzil acids. The initial cycloaddition products, β-lactones, are isolated in some instances while some β-lactones spontaneously underwent decarboxylation and could not be isolated.
The ketene intermediate was demonstrated in the intramolecular reaction of benzil acids or ketoacids with sodium acetate and acetic anhydride. It is suggested that sodium acetate and acetic anhydride could serve as a source for the generation of ketenes directly from certain organic acids. The treatment of ketoacids with acetic anhydride and sodium acetate provides a simpler procedure to prepare benzofurans than going through the acid chloride with subsequent triethylamine dehydrochlorination to give the ketenes.
N-Ary1-N-alkylaminoketenes were prepared for the first time from the corresponding glycine derivatives by using p-toluenesulfonyl chloride and triethylamine. These aminoketenes underwent in situ cycloadditions with cyclopentadiene, cycloheptene and cyclooctenes to yield only the endo -bicyclobutanones. The cycloheptene and cyclooctene cycloaddition products underwent dehydrogenation under the reaction conditions to yield bicycloenamines. A mechanism is proposed for this dehydrogenation involving a radical cation of the arylalkylamine. (N-Phenyl-N-methyl) aminomethylketene was also prepared and found to undergo an intramolecular Friedel-Crafts type acylation to yield an indole derivative when prepared by the acetic anhydride, sodium acetate method.
The in situ cycloaddition of N-aryl-N-alkyl aminoketenes with various imines was found to form predominately cis-3-amino-2-azetidinones. A mechanism involving a dipolar intermediate is provided whereby the structure of the intermediate is determined by both electronic and steric effects. The stereochemistry of the resulting β-lactams is dependent upon the structure of the dipolar intermediate.

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iv, 116 leaves: ill.

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  • May 1989

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  • Aug. 22, 2014, 6 p.m.

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  • Oct. 14, 2015, 2:27 p.m.

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Gu, Yi Qi. Intramolecular [2+2] Cycloadditions of Phenoxyketenes and Intermolecular [2+2] Cycloadditions of Aminoketenes, dissertation, May 1989; Denton, Texas. (digital.library.unt.edu/ark:/67531/metadc332334/: accessed September 19, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; .