Synthesis and crystal structures of 2-(ferrocenylcarbonyl)benzoic acid and 3-ferrocenylphthalide

Pokharel, Uttam R.; Bergeron, Jonathan T; Fronczek, Frank R.

doi:10.1107/s2056989020008452

Cited by 2 publications

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References 21 publications

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“…2-(Ferrocenoyl)benzoic acid (3a). The compound was synthesized by following the procedure reported in the literature [20].…”

Section: Methodsmentioning

confidence: 99%

Lactonization of α-Ferrocenyl Ketocarboxylic Acids via Nucleophilic Attack of Carbonyl Oxygen

Pokharel,

Curole,

Andras

et al. 2024

Crystals

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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, on 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.

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“…2-(Ferrocenoyl)benzoic acid (3a). The compound was synthesized by following the procedure reported in the literature [20].…”

Section: Methodsmentioning

confidence: 99%

Lactonization of α-Ferrocenyl Ketocarboxylic Acids via Nucleophilic Attack of Carbonyl Oxygen

Pokharel,

Curole,

Andras

et al. 2024

Crystals

Self Cite

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show abstract

Lactonization of α-Ferrocenyl Ketocarboxylic Acids via Nucleophilic Attack of Carbonyl Oxygen

Pokharel,

Curole,

Andras

et al. 2024

Preprint

View full text Add to dashboard Cite

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.

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Synthesis and crystal structures of 2-(ferrocenylcarbonyl)benzoic acid and 3-ferrocenylphthalide

Abstract: The title compounds, 2-(ferrocenylcarbonyl)benzoic acid, [Fe(C5H5)(C13H9O3)], 1, and 3-ferrocenylphthalide [systematic name: 3-ferrocenyl-2-benzofuran-1(3H)-one], [Fe(C5H5)(C13H9O2)], 2, have been synthesized and structurall… Show more

Cited by 2 publications

References 21 publications

Lactonization of α-Ferrocenyl Ketocarboxylic Acids via Nucleophilic Attack of Carbonyl Oxygen

Lactonization of α-Ferrocenyl Ketocarboxylic Acids via Nucleophilic Attack of Carbonyl Oxygen

Lactonization of α-Ferrocenyl Ketocarboxylic Acids via Nucleophilic Attack of Carbonyl Oxygen

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