Electrophilic trifluoromethylation reactions have been the latest approach to achieve the fluoroalkylation of compounds with newly‐discovered reagents, such as the Togni’s (1‐trifluoromethyl‐1,2‐benziodoxol‐3‐(1 H)‐one), Umemoto’s (S‐(trifluoromethyl)dibenzothiophenium tetrafluoroborate), Yagupolskii’s (S‐(trifluoromethyldiarylsulfonium salts), Shreeve’s (S‐(trifluoromethyl)dibenzothiophenium triflate), and Shibata’s (trifluoromethylsulfoximine salts) reagents. All these reagents produce an electrophilic trifluoromethylating (CF₃⁺) species that undergoes reaction with nucleophiles. In addition, these latter reactive species (i.e. CF₃⁺) can undergo electron‐transfer (ET) processes affording CF₃^⋅ radicals that expand the scope to substrates other than conventional nucleophiles that can undergo reaction. In this Review, we shall discuss the trifluoromethylation reactions of diverse families of organic substrates of biological interest as a means to comparing the reagents scope and best reaction conditions. Some, though not all, of these reactions require the assistance of metal or organometallic catalysts. Some require additives and catalysts to promote the fluoroalkylation reaction, but invariably all are initiated and carried out by electrophilic trifluoromethylating species.

中文翻译：

---

三氟甲基化反应与亲电三氟甲基化试剂的最新进展

亲电子三氟甲基化反应是使用新发现的试剂实现化合物的氟烷基化的最新方法，例如Togni's（1-trifluoromethyl-1,2-benziodoxol-3（1 H）-one），Umemoto's（S-（三氟甲基）二苯并噻吩鎓四氟硼酸盐），Yagupolskii的（S-（trifluoromethyldiarylsulfonium盐），史瑞夫的（S-（三氟甲基）二苯并噻吩三氟甲磺酸酯），和柴田的（trifluoromethylsulfoximine盐）的试剂。这些试剂产生亲电三氟甲基化（CF ₃ ⁺）物种经历反应与亲核试剂。此外，这些后面的反应性物种（即CF ₃ ⁺）可以进行电子转移（ET）处理，得到CF ₃ ^⋅能够将范围扩大到可进行反应的常规亲核试剂以外的底物的自由基。在本综述中，我们将讨论具有生物学意义的各种有机底物家族的三氟甲基化反应，作为比较试剂范围和最佳反应条件的一种方法。这些反应中的一些（尽管不是全部）需要金属或有机金属催化剂的协助。一些化合物需要添加剂和催化剂来促进氟烷基化反应，但始终都是由亲电子的三氟甲基化物质引发和进行的。