Oxidative C–O Coupling: Radical and Ionic Pathways of Reaction in Bu4NI/t-BuOOH System

IF 0.8 4区化学 Q4 CHEMISTRY, MULTIDISCIPLINARY Doklady Chemistry Pub Date : 2022-11-02 DOI:10.1134/S0012500822600092

E. R. Lopat’eva, I. B. Krylov, I. V. Kuzmin, S. V. Suchkov, A. O. Terent’ev

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Abstract

The Bu₄NI/t-BuOOH oxidative system is widely used in organic synthesis, but mechanistic principles underlying its reactivity are only partially explored. In this work, drawing on the example of the oxidative C–O coupling reaction between compounds with a carbonyl group and (or) a benzyl moiety with N-hydroxyphthalimide, it has been discovered that the coupling with the CH-acidic fragment of the carbonyl group proceeds via ionic mechanism, and the coupling with the benzyl fragment proceeds via radical mechanism. When dimethylacetamide is used as a solvent, the ionic process with the participation of the carbonyl group prevails, while in MeCN the radical process involving the benzyl moiety is realized along with the ionic process. For the oxidative C–O coupling with participation of the benzyl moiety without affecting the α-CH fragment of the carbonyl group, it is advisable to use PhI(OAc)₂, Ce(NH₄)₂(NO₂)₆, or t‑BuOOt-Bu as oxidants for which only radical pathway is characteristic.

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氧化C-O偶联:Bu4NI/t-BuOOH体系反应的自由基和离子途径

Bu4NI/t-BuOOH氧化体系在有机合成中被广泛应用，但其反应性的机制原理仅被部分探索。本文以含羰基和(或)苯基的化合物与n -羟基邻苯二胺之间的氧化C-O偶联反应为例，发现羰基ch -酸性片段的偶联是通过离子机制进行的，而苯基片段的偶联是通过自由基机制进行的。当二甲基乙酰胺作为溶剂时，羰基参与的离子过程占优势，而在MeCN中，涉及苄基部分的自由基过程与离子过程一起实现。对于苯基部分参与而不影响羰基α-CH片段的C-O氧化偶联，建议使用仅以自由基途径为特征的PhI(OAc)2、Ce(NH4)2(NO2)6或t- BuOOt-Bu作为氧化剂。

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来源期刊

Doklady Chemistry 化学-化学综合

CiteScore

1.20

自引率

12.50%

发文量

审稿时长

6-12 weeks

期刊介绍： Doklady Chemistry is a journal that publishes new research in chemistry and chemical engineering of great significance. Initially the journal was a forum of the Russian Academy of Science and published only best contributions from Russia in the form of short articles. Now the journal welcomes submissions from any country in the English or Russian language. Every manuscript must be recommended by Russian or foreign members of the Russian Academy of Sciences.