AbstractRadical trifluoromethoxylation is an attractive approach to prepare compounds featuring the important OCF3 group, however most existing methods have focused on aromatic substrates. Here, we report novel methodologies with alkenyl substrates employing bis(trifluoromethyl)peroxide (BTMP) as a practical and comparatively atom economical trifluoromethoxylating reagent. With silyl enol ether substrates, switching reaction solvent allows for the synthesis of either α‐(trifluoromethoxy)ketone products or unprecedented alkenyl‐OCF3 species. Furthermore, allyl silanes have been employed as substrates for the first time, affording allyl(trifluoromethyl)ether products in good yields. In each case, the methods operate at room temperature without large excesses of the alkene substrate while, in contrast to previous radical trifluoromethoxylation reactions, no catalyst, light or other activators are required.

中文翻译：

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硅烯醇醚和烯丙基硅烷与双（三氟甲基）过氧化物的无催化剂三氟甲氧基化

摘要自由基三氟甲氧基化是制备具有重要 OCF 的化合物的一种有吸引力的方法3然而，大多数现有方法都集中在芳香族底物上。在这里，我们报告了使用双（三氟甲基）过氧化物（BTMP）作为实用且相对原子经济的三氟甲氧基化试剂的烯基底物的新方法。使用硅烯醇醚底物，切换反应溶剂可以合成 α-(三氟甲氧基)酮产品或前所未有的烯基-OCF3物种。此外，首次采用烯丙基硅烷作为底物，以良好的产率提供烯丙基（三氟甲基）醚产品。在每种情况下，该方法都在室温下进行，没有大量过量的烯烃底物，同时与之前的自由基三氟甲氧基化反应相比，不需要催化剂、光或其他活化剂。