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Theoretical study on the mechanism of the benzaldehyde deoxyfluorination by sulfuryl fluoride and tetramethylammonium fluoride
Journal of Physical Organic Chemistry ( IF 1.9 ) Pub Date : 2022-05-24 , DOI: 10.1002/poc.4389
Chenxi Sheng 1 , Zhewei Li 1 , Min Pu 1 , Ming Lei 1
Journal of Physical Organic Chemistry ( IF 1.9 ) Pub Date : 2022-05-24 , DOI: 10.1002/poc.4389
Chenxi Sheng 1 , Zhewei Li 1 , Min Pu 1 , Ming Lei 1
Affiliation
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Organic fluoride compounds have a potential widely application in pharmaceutical, chemical, and material industries. The deoxyfluorination of C=O bonds is one of important ways to synthesize the organic fluorides. Recently, one efficient aldehyde deoxyfluorination strategy by sulfuryl fluoride (SO2F2) and tetramethylammonium fluoride (TMAF) under mild condition was proposed with low cost and high yield, and SO2F2 was produced by the reaction of 1,1′-sulfonyldiimidazole (SDI) and KF in formic acid solvent. Herein, a density functional theory (DFT) study was performed to investigate the nature of this reaction including the SO2F2 formation and the aldehyde deoxyfluorination. The calculated results indicate that in the SO2F2 formation, the formic acid plays an important role and participates in the reaction with SDI and KF to transfer proton and convert imidazole cation into imidazole, and in the aldehyde deoxyfluorination by SO2F2 and TMAF, this study points out that there are two C–F coupling steps in this process, and the second one along a SN2 pathway is the rate-determining step with a free energy barrier of 9.6 kcal/mol. The fluoride anions (F−) come from TMAF as fluorination reagent, which agree well with experimental results. And SO2F2 acts as deoxidization reagent. In comparison with the benzaldehyde deoxyfluorination by diethylaminosulfur trifluoride (DAST), the aldehyde deoxyfluorination strategy by SO2F2 and TMAF owns thermodynamic and kinetic advantages. This theoretical study could provide theoretical insights to design new reagent for the deoxyfluorination of C=O bonds.
中文翻译：
硫酰氟和四甲基氟化铵脱氧氟化苯甲醛机理的理论研究
有机氟化合物在医药、化工和材料工业中具有广泛的应用潜力。C=O键的脱氧氟化是合成有机氟化物的重要途径之一。最近，提出了一种低成本、高收率的硫酰氟（SO 2 F 2 ）和四甲基氟化铵（TMAF）在温和条件下进行醛脱氧氟化的有效策略，通过1,1'-反应制得SO 2 F 2 。甲酸溶剂中的磺酰二咪唑 (SDI) 和 KF。在此，进行了密度泛函理论 (DFT) 研究以研究该反应的性质，包括 SO 2 F 2生成和醛脱氧氟化。计算结果表明，在SO 2 F 2生成过程中，甲酸起重要作用，参与了与SDI和KF的转移质子和将咪唑阳离子转化为咪唑的反应，以及SO 2 F 2和醛的脱氧氟化反应。 TMAF，本研究指出该过程中有两个 C-F 耦合步骤，第二个沿 S N 2 途径的步骤是自由能垒为 9.6 kcal/mol 的速率决定步骤。氟化物阴离子（F -）来自TMAF作为氟化试剂，与实验结果吻合良好。和 SO 2 F 2作为脱氧剂。与二乙氨基三氟化硫（DAST）的苯甲醛脱氧氟化相比，SO 2 F 2和TMAF的醛脱氟策略具有热力学和动力学优势。该理论研究可为设计用于 C=O 键脱氧氟化的新试剂提供理论见解。
更新日期：2022-05-24
中文翻译：
硫酰氟和四甲基氟化铵脱氧氟化苯甲醛机理的理论研究
有机氟化合物在医药、化工和材料工业中具有广泛的应用潜力。C=O键的脱氧氟化是合成有机氟化物的重要途径之一。最近，提出了一种低成本、高收率的硫酰氟（SO 2 F 2 ）和四甲基氟化铵（TMAF）在温和条件下进行醛脱氧氟化的有效策略，通过1,1'-反应制得SO 2 F 2 。甲酸溶剂中的磺酰二咪唑 (SDI) 和 KF。在此，进行了密度泛函理论 (DFT) 研究以研究该反应的性质，包括 SO 2 F 2生成和醛脱氧氟化。计算结果表明，在SO 2 F 2生成过程中，甲酸起重要作用，参与了与SDI和KF的转移质子和将咪唑阳离子转化为咪唑的反应，以及SO 2 F 2和醛的脱氧氟化反应。 TMAF，本研究指出该过程中有两个 C-F 耦合步骤，第二个沿 S N 2 途径的步骤是自由能垒为 9.6 kcal/mol 的速率决定步骤。氟化物阴离子（F -）来自TMAF作为氟化试剂，与实验结果吻合良好。和 SO 2 F 2作为脱氧剂。与二乙氨基三氟化硫（DAST）的苯甲醛脱氧氟化相比，SO 2 F 2和TMAF的醛脱氟策略具有热力学和动力学优势。该理论研究可为设计用于 C=O 键脱氧氟化的新试剂提供理论见解。
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