The trifluoroethyl aryl ethers are important motifs in drug molecules. However, a report devoted specifically to the study of transition-metal-catalyzed C–H trifluoroethoxylation has not been reported to date. A protocol of Pd(II)-catalyzed o-C–H trifluoroethoxylation of a broad range of benzoic acid derivatives (i.e., N-sulfonylbenzamides) has been developed. This method is also applied to the formal synthesis of the drug molecule flecainide, wherein the first m-C–H trifluoroethoxylation is also exemplified.

A novel readily available bidentate 2-methylsulfinyl isobutyramide directing group has been developed for benzylamine derivatives. It promoted ortho-C–H arylation and iodination of various substrates in good to excellent yields. The auxiliary is promising to be used in organic synthesis due to its versatility and convenient preparation from inexpensive materials.

AbstractCarbon dioxide (CO2), a readily available, non-toxic, and inexpensive greenhouse gas, is an ideal reagent for carbamate synthesis. For the first time, CO2 has been efficiently incorporated into a novel nitrile-containing directing group (DG) for meta-C–H activation of anilines under mild conditions. Thus, various aniline derivatives were meta-olefinated with palladium(II) acetate. meta-C–H acetoxylation was also feasible and the carbamate DG could be easily removed under basic conditions. The practicality of substrate preparation, functional group tolerance, and versatility of this method make it a valuable addition to the meta-C–H functionalization of anilines.

Site selectivity control is of vital importance in the direct functionalization of inert C–H bonds. Reported here is a novel example of remote regiodivergent ortho- and meta-C–H bond functionalizations of phenylethylamine derivatives by using a novel 2-cyanobenzoyl group as the original directing functionality, where the regioselectivity was adjusted by a methylation. The potential of the method was exemplified by sequential functionalizations of both ortho- and meta-C–H bonds of a phenylethylamine derivative in a streamlined manner.

Site selectivity control is of vital importance in the direct functionalization of inert C–H bonds. Reported here is a novel example of remote regiodivergent ortho- and meta-C–H bond functionalizations of phenylethylamine derivatives by using a novel 2-cyanobenzoyl group as the original directing functionality, where the regioselectivity was adjusted by a methylation. The potential of the method was exemplified by sequential functionalizations of both ortho- and meta-C–H bonds of a phenylethylamine derivative in a streamlined manner.

A novel readily available bidentate 2-methylsulfinyl isobutyramide directing group has been developed for benzylamine derivatives. It promoted ortho-C–H arylation and iodination of various substrates in good to excellent yields. The auxiliary is promising to be used in organic synthesis due to its versatility and convenient preparation from inexpensive materials.