CF₃‐Carbenoid C–H Functionalization of (Hetero)arenes under Chelation‐Controlled Rh^III Catalysis

Abstract

An efficient method for the CF3‐carbenoid C–H functionalization of benzenes and indoles using readily available methyl 3,3,3‐trifluoro‐2‐diazopropionate as a cross‐coupling partner under chelation‐controlled RhIII catalysis has been developed. The reactions proceeded smoothly with high regioselectivity in a few hours and allowed the simultaneous introduction of CF3 and carboxylate functions into the 2‐position of directing‐group‐containing benzenes and indoles.

Progress in Diazo Compounds Mediated Transition-Metal-Catalyzed C—H Alkylation

“…许多有机分子因具有三氟甲基结构而具有特殊的 活性, 因此, 将三氟甲基官能团引入到医药, 农药及新 型功能有机分子中具有特别重要的意义 [30] . 2015 年, Osipov 等 [31] 2015 年 Wang 小组 [32] 使用价格低廉的 Cp*Co(CO)I 2 / AgSbF 6 作为催化剂, 在吡唑基团的导向作用下, 可以将 苯环上的 C-H 键转化为烷基(Scheme 12). 在嘧啶基团 的导向作用下, 可以实现吲哚 C(2)-位的 C-H 烷基化反 应.…”

Catalytic functionalization of low reactive C(sp3)–H and C(sp2)–H bonds of alkanes and arenes by carbene transfer from diazo compounds

“…Scheme 16 shows the development of this methodology by the groups of Yu, 57 Rovis, 58 Glorius, 59 Wang 60 and Osipov. 61 In all cases, a net incorporation of the carbene group at the ortho position is observed, albeit in some cases a subsequent transformation involving the directing group takes place, providing molecular complexity beyond the mere C-H functionalization.…”

“…49 At this stage, it is worth noting the work carried out by McKervey and co-workers showing the arrangement of cycloheptatrienes into the insertion products in the presence of acid. 50 61 In all cases, a net incorporation of the carbene group at the ortho position is observed, albeit in some cases a subsequent transformation involving the directing group takes place, providing molecular complexity beyond the mere C-H functionalization.…”

Recent advances in transition-metal catalyzed directed C–H functionalization with fluorinated building blocks

“…N -arylpyrazoles, aryl ketone methoximes and N -(pyrimidin-2-yl)-indoles) using a Rh( iii ) catalyst. 80 The optimized reaction involves [RhCp*Cl 2 ] 2 (2 mol%) and 10 mol% AgOTf in DCE at 80 °C for 4 h to afford the desired C–H alkylation product 6 containing both the trifluoromethyl substituent and carboxyl functionality. The reaction conditions were found to be the same for all three substrates with the only difference being in the use of a Ag( i ) additive.…”