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Critical Assessment of the Reducing Ability of Breslow-type Derivatives and Implications for Carbene-Catalyzed Radical Reactions*.

ABSTRACT: We report the synthesis of acyl azolium salts stemming from thiazolylidenes C_NS , triazolylidenes C_TN _, mesoionic carbenes C_MIC and the generation of their corresponding radicals and enolates, covering about 60 Breslow-type derivatives. This study highlights the role of additives in the redox behavior of these compounds and unveils several critical misconceptions about radical transformations of aldehyde derivatives under N-heterocyclic carbene catalysis. In particular, the reducing ability of enolates has been dramatically underestimated in the case of biomimetic C_NS . In contrast with previous electrochemical studies, we show that these catalytic intermediates can transfer electrons to iodobenzene within minutes at room temperature. Enols derived from C_MIC are not the previously claimed super electron donors, although enolate derivatives of C_NS and C_MIC are powerful reducing agents.

SUBMITTER: Delfau L

PROVIDER: S-EPMC9299025 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature

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Critical Assessment of the Reducing Ability of Breslow-type Derivatives and Implications for Carbene-Catalyzed Radical Reactions*.

Delfau Ludivine L Nichilo Samantha S Molton Florian F Broggi Julie J Tomás-Mendivil Eder E Martin David D

Angewandte Chemie (International ed. in English) 20211115 51

We report the synthesis of acyl azolium salts stemming from thiazolylidenes CNS , triazolylidenes CTN, mesoionic carbenes CMIC and the generation of their corresponding radicals and enolates, covering about 60 Breslow-type derivatives. This study highlights the role of additives in the redox behavior of these compounds and unveils several critical misconceptions about radical transformations of aldehyde derivatives under N-heterocyclic carbene catalysi ...[more]

PMID: 34651408

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Project description:We investigated the reactions of the hydroxyl radical (OH) with cyclopentenone derivatives and cyclopentanone in a quasi-static reaction cell at 4 Torr across a 300-500 K temperature range. The OH radicals were generated using pulsed laser photolysis of hydrogen peroxide vapors, and the ketone reactants were introduced in excess. The relative concentrations of the radicals were monitored as a function of reaction time using laser-induced fluorescence. At room temperature, the reaction rate coefficients were measured to be 1.2(±0.1) × 10-11 cm3 s-1 for reaction with 2-cyclopenten-1-one (R1); 1.7(±0.2) × 10-11 cm3 s-1 for reaction with 2-methyl-2-cyclopenten-1-one (R2); and 4.4(±0. 7) × 10-12 cm3 s-1 for reaction with 3-methyl-2-cyclopenten-1-one (R3). Over the experimental temperature range, the rate coefficients can be fitted with the modified Arrhenius expressions k1(T) = 1.2 × 10-11 (T/300)0.26 exp (6.7 kJ mol-1/R {1/T - 1/300}) cm3 s-1, k2(T) = 1.7 × 10-11 (T/300)6.4 exp (27.6 kJ mol-1/R {1/T - 1/300}) cm3 s-1, k3(T) = 4.4 × 10-12 (T/300)17.8 exp (57.8 kJ mol-1/R {1/T - 1/300}) cm3 s-1. In the cases of 2-cyclopenten-1-one and 2-methyl-2-cyclopenten-1-one, the temperature dependence of the rate coefficients is similar to that calculated or measured for noncyclic conjugated ketones. We also found that the reaction with 3-methyl-2-cyclopenten-1-one was slower, with rate coefficients similar to those measured for the reaction with the saturated cyclic ketone cyclopentanone. To discuss the experimental data, we use potential energy surfaces (PES) calculated at the CCSD(T)/cc-pVTZ//M06-2X/6-311+G** level of theory. RRKM-based Master equation calculations were also performed to infer the most likely reaction products over a wide range of temperatures and pressures. We suggest that both abstraction and addition mechanisms contribute to the overall OH removal, forming radical products stabilized by resonance. We also discuss the relevance for combustion and atmospheric chemistry.

Dataset Information

Critical Assessment of the Reducing Ability of Breslow-type Derivatives and Implications for Carbene-Catalyzed Radical Reactions*.

Publications

Critical Assessment of the Reducing Ability of Breslow-type Derivatives and Implications for Carbene-Catalyzed Radical Reactions*.

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