Pokharel, U.; Curole, B.; Andras, A.; LeBlanc, B.; Fronczek, F. Lactonization of α-Ferrocenyl Ketocarboxylic Acids via Nucleophilic Attack of Carbonyl Oxygen. Crystals 2024, 14, 548, doi:10.3390/cryst14060548.
Pokharel, U.; Curole, B.; Andras, A.; LeBlanc, B.; Fronczek, F. Lactonization of α-Ferrocenyl Ketocarboxylic Acids via Nucleophilic Attack of Carbonyl Oxygen. Crystals 2024, 14, 548, doi:10.3390/cryst14060548.
Pokharel, U.; Curole, B.; Andras, A.; LeBlanc, B.; Fronczek, F. Lactonization of α-Ferrocenyl Ketocarboxylic Acids via Nucleophilic Attack of Carbonyl Oxygen. Crystals 2024, 14, 548, doi:10.3390/cryst14060548.
Pokharel, U.; Curole, B.; Andras, A.; LeBlanc, B.; Fronczek, F. Lactonization of α-Ferrocenyl Ketocarboxylic Acids via Nucleophilic Attack of Carbonyl Oxygen. Crystals 2024, 14, 548, doi:10.3390/cryst14060548.
Abstract
The effects of the ferrocenyl moiety to enhance the nucleophilicity of the carbonyl group, situated at its adjacent position, have been explored in a series of α-ferrocenyl ketocarboxylic acids. In the presence of trifluoroacetic anhydride, 3-ferrocenoylpropionic acid and 4-ferrocenoylbutyric acid gave 5-ferrocenyl-4-trifluoroacetyl-2(3H)-furanone and 6-ferrocenyl-5-trifluoroacetyl-3,4-dihydropyran-2-one, respectively. Under similar reaction conditions, 2-ferrocenylcarbonylbenzoic acid, a keto carboxylic acid without a β-hydrogen, gave a dimerized lactone, 3,3’-diferrocenyl-3,3’-diphthalide possibly due to radical coupling. The nucleophilic attack of carbonyl oxygen, activated by the ferrocenyl moiety, to the carboxylic carbon, is assumed to be the crucial mechanistic step in forming these lactones. When the carbonyl group was reduced to an alcohol to break its conjugation with the ferrocenyl moiety, saturated lactones were isolated after the acidic workup. These results indicate that the α-ferrocenyl carbinols readily undergo solvolysis under acidic conditions, giving ferrocenylcarbenium ions, which are attacked by the carboxy oxygen to give lactones.
Chemistry and Materials Science, Organic Chemistry
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