A Twist of the Twist Mechanism, 2-Iodoxybenzoic Acid (IBX)-Mediated Oxidation of Alcohol Revisited: Theory and Experiment,Organic Letters

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A Twist of the Twist Mechanism, 2-Iodoxybenzoic Acid (IBX)-Mediated Oxidation of Alcohol Revisited: Theory and Experiment
Organic Letters ( IF 4.9 ) Pub Date : 2017-11-22 00:00:00 , DOI: 10.1021/acs.orglett.7b03167
Heming Jiang ₁ , Tian-Yu Sun _{1,

2} , Xiao Wang ₂ , Yaoming Xie ₂ , Xinhao Zhang ₁ , Yun-Dong Wu _{1,

3} , Henry F. Schaefer ₂

Affiliation

2-Iodoxybenzoic acid (IBX) is an important species for the oxidation of alcohols to aldehydes or ketones. An often-cited mechanism involving a hypervalent twist as the rate-determining step (RDS) is inconsistent with kinetic isotope effect (KIE) experiments. The computations with larger basis sets reveal that the reductive elimination involving the C–H bond cleavage is the RDS (rate-determining step). Further computational/experimental studies suggest that the reactivity can be improved by adjusting the trans influence with Lewis acids.

中文翻译：

扭转机理的扭转，2-碘氧苯甲酸（IBX）介导的醇氧化研究：理论与实验

2-碘氧基苯甲酸（IBX）是将醇氧化为醛或酮的重要物质。经常引用的机制涉及速率决定步骤（RDS）的高价扭曲与动力学同位素效应（KIE）实验不一致。具有较大基础集的计算表明，涉及C–H键断裂的还原消除是RDS（速率确定步骤）。进一步的计算/实验研究表明，可以通过调节路易斯酸的反式影响来提高反应性。

更新日期：2017-11-22

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