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Efficient synthesis of o-borylphenols is achieved through the Ru-catalyzed regio- and site-selective sp2 C-H borylation of aryl diphenylphosphinites followed by removal of the phosphorus directing group. A successful application to aryl phosphites enables practical one-pot borylation of phenols, demonstrating high synthetic utility of this protocol.

A PGeP-pincer palladium-catalyzed hydrocarboxylation of styrenes to obtain pharmaceutically important α-arylpropionic acid derivatives was achieved using a formate salt as both a reductant and a CO 2 source. The reaction was also applicable to vinylsulfone and acrylates. Isotope labeling experiments demonstrated that a CO 2 -recycling mechanism is operative through generation and reaction of a benzylpalladium complex as a carbon nucleophile. This protocol has realized a mild and atom economical CO 2 -fixation reaction without the necessity of using strong metallic reductants.

A visible light driven catalytic cycle for hydrocarboxylation of alkenes with CO 2 was established using a combination of a Rh(i) complex as a carboxylation catalyst and [Ru(bpy) 3 ] 2+ (bpy = 2,2'- bipyridyl) as a photoredox catalyst. Two key steps, the generation of Rh(i) hydride species and nucleophilic addition of π-benzyl Rh(i) species to CO 2 , were found to be mediated by light.

An efficient, regioselective synthesis of fluorine-substituted arylboronic esters was achieved through fluorine-controlled C-H borylation of arenes with diboron catalyzed by a PSiN-platinum complex. The promising utility of the PSiN-platinum catalyst and its unique regioselectivity were demonstrated for the first time, which would complement the well-developed Ir-catalyzed C-H borylation.

Direct carboxylation of simple arenes under atmospheric pressure of CO2 is achieved through a rhodium-catalyzed C-H bond activation without the assistance of a directing group. Various arenes such as benzene, toluene, xylene, electron-rich or electron-deficient benzene derivatives, and heteroaromatics are directly carboxylated with high TONs.