In this study high‐valent Cu(III) trifluoromethyl compounds in combination with DMSO is shown to be an efficient and mild oxidizing system for the conversion of alcohols to ketones (aldehydes as well). Trifluoromethoxylated sulfonium species is proposed to be initially formed that engages in crucial steps of alkoxy replacement at sulfonium center and deprotonative collapse of the resulting alkoxysulfonium intermediate in the presence of a base. This reaction is highly selective without over‐oxidation, and can tolerate a broad range of functional groups owing to mild oxidizing ability of the Cu(III)‐CF3/DMSO system and the inert N2 conditions. This method can be applied to the synthesis and functionalization of commercial drug compounds. This study illustrates an unusual reactivity property of high‐valent Cu(III) trifluoromethyl compounds beyond the conventional CF3 group transfer reactivity, and opens up new opportunities for developing novel reactions of Cu(III)‐CF3 compounds. The combined use of high‐valent Cu(III)‐CF3 compound and DMSO is anticipated to find more applications to develop other novel and useful oxidation reactions.

中文翻译：

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Cu(III)-CF3 化合物激活的 DMSO：一种将醇转化为酮的高效氧化试剂

在这项研究中，高价三氟甲基铜 (III) 化合物与 DMSO 结合被证明是一种有效且温和的氧化系统，可将醇转化为酮（也包括醛）。提议最初形成三氟甲氧基化锍物种，其参与锍中心的烷氧基取代和所得烷氧基锍中间体在碱存在下的去质子塌陷的关键步骤。该反应具有高度选择性，不会过度氧化，并且由于 Cu(III)-CF3/DMSO 系统的温和氧化能力和惰性 N2 条件，可以耐受广泛的官能团。该方法可应用于商业药物化合物的合成和功能化。这项研究说明了高价 Cu(III) 三氟甲基化合物超越传统 CF3 基团转移反应性的不寻常反应特性，并为开发 Cu(III)-CF3 化合物的新型反应开辟了新的机会。高价 Cu(III)-CF3 化合物和 DMSO 的联合使用有望找到更多应用来开发其他新颖且有用的氧化反应。