Oxidative Trifluoromethylation of Arylboronates with Shelf‐Stable Potassium (Trifluoromethyl)trimethoxyborate

Abstract

Introducing CF3: Arylboronic acid pinacol esters are converted into the corresponding benzotrifluorides with the easy‐to‐use one‐component trifluoromethylating reagent potassium (trifluoromethyl)trimethoxyborate, mediated by copper acetate under an oxygen atmosphere (see scheme).

Recent advances in the trifluoromethylation methodology and new CF3-containing drugs

“…The first examples reported consisted in the copper-mediated reaction with CF 3 SiMe 3 , in the presence of oxidants such as Ag 2 CO 3 [16] or oxygen [17] (Scheme 1, path c). Soon afterward, a plethora of related protocols have increased the potential of aryl boronic acids employing different sources of CF 3 , which include other nucleophilic (potassium (trifluoromethyl)trialkoxyborates [18]), electrophilic (trifluoromethyl sulfonium salts [19]), or radical reagents (NaSO 2 CF 3 /TBHP [20]) as well as fluoroform [21]. From these findings, catalytic procedures have also been developed, by using CF 3 SiMe 3 [22], Togni's reagent [23], Umemoto's reagent [24], CF 3 I/visible light [25] or again NaSO 2 CF 3 /TBHP [26].…”

Biocatalytic trifluoromethylation of unprotected phenols

“…Among all fluorine-containing moieties, the trifluoromethyl group is privileged4, and trifluoromethylated arenes are of interest for agrochemicals, pharmaceuticals and advanced materials5. Several excellent methods to provide structurally diverse CF 3 -building blocks have been elaborated678: common strategies to introduce the CF 3 -group into aromatic compounds involve metal-mediated/catalysed functional group interconversions910 where halogens111213, boronic acids141516, boronates1718 and even amines1920 are replaced by nucleophilic, electrophilic or radical CF 3 -sources (Fig. 1a).…”

Recent Advances of Trifluoromethylation

“…2011 年, 清华大学刘磊教授 [42] 和北京大学的王剑 波教授等 [43] 发现在铜催化下, 亲电三氟甲基化试剂与 未活化的烯烃反应可生成三氟甲基化的烯丙基化合物 (Scheme 13), 他们对反应机理也进行了探索. [26] , Hartwig [21] 和 Gooβen 等 [25] 进一步开展硼酸和硼酯的氧化三氟甲基 化反应; 刘磊 [38] 、沈其龙 [39] 和肖吉昌等 [40] 研究了芳基硼 酸与亲电三氟甲基化试剂的反应. …”