New ligands for the iridium‐catalyzed C(sp3)−H borylation of aliphatic compounds were established. In sharp contrast to 6‐methyl‐2,2′‐bipyridine and 6‐isobutyl‐2,2′‐bipyridine, 2,2′‐bipyridine and 1,10‐phenanthroline derivatives bearing a hydrosilylmethyl group (which would give a thermally stable NNSi pincer complex) served as suitable ligands for the reaction. Among them, a phenanthroline‐based NNSi pincer ligand was shown to be an excellent ligand, and various aliphatic compounds were efficiently converted to the corresponding borylated products using the Ir/NNSi pincer catalyst system. The NNSi pincer ligand showed unique selectivity and enabled the iridium‐catalyzed C(sp3)−H borylation using pinacolborane [H−B(pin)] instead of B2(pin)2. The formation of an iridium complex bearing a quinoline‐based NNSi pincer ligand from [IrCl(cod)]2 was observed, and the catalytic activity of the complex was demonstrated.

A regioselective radical C-H trifluoromethylation of aromatic compounds was developed using cyclodextrins (CDs) as additives. The C-H trifluoromethylation proceeded with high regioselectivity to afford the product in good yield, even on the gram scale. In the presence of CDs, some substrates underwent a single trifluoromethylation selectively, whereas mixtures of single-and double-trifluoromethylated products were formed in the absence of the CD. 1 H NMR experiments indicated that the regioselectivity was controlled by the inclusion of a substrate inside the CD cavity.

New ligands for the iridium-catalyzed C-(sp 3 )À H borylation of aliphatic compounds were established. In sharp contrast to 6-methyl-2,2'-bipyridine and 6-isobutyl-2,2'-bipyridine, 2,2'-bipyridine and 1,10-phenanthroline derivatives bearing a hydrosilylmethyl group (which would give a thermally stable NNSi pincer complex) served as suitable ligands for the reaction. Among them, a phenanthroline-based NNSi pincer ligand was shown to be an excellent ligand, and various aliphatic compounds were efficiently converted to the corresponding borylated products using the Ir/NNSi pincer catalyst system. The NNSi pincer ligand showed unique selectivity and enabled the iridium-catalyzed C(sp 3 )À H borylation using pinacolborane [HÀ B(pin)] instead of B 2 (pin) 2 . The formation of an iridium complex bearing a quinoline-based NNSi pincer ligand from [IrCl(cod)] 2 was observed, and the catalytic activity of the complex was demonstrated.

A regioselective radical C–H trifluoromethylation of aromatic compounds was developed using cyclodextrins (CDs) as additives. The C–H trifluoromethylation proceeded with high regioselectivity to afford the product in good yield, even on the gram scale. In the presence of CDs, some substrates underwent a single trifluoromethylation selectively, whereas mixtures of single- and double-trifluoromethylated products were formed in the absence of the CD. ¹H NMR experiments indicated that the regioselectivity was controlled by the inclusion of a substrate inside the CD cavity.

A regioselective radical C–H trifluoromethylation of aromatic compounds was developed using cyclodextrins (CDs) as additives. The C–H trifluoromethylation proceeded with high regioselectivity to afford the product in good yield, even on the gram scale. In the presence of CDs, some substrates underwent a single trifluoromethylation selectively, whereas mixtures of single- and double-trifluoromethylated products were formed in the absence of the CD. ¹H NMR experiments indicated that the regioselectivity was controlled by the inclusion of a substrate inside the CD cavity.