Rapid Synthesis of γ-Arylated Carbonyls Enabled by the Merge of Copper- and Photocatalytic Radical Relay Alkylarylation of Alkenes.

The development of mild and practical methods for the γ-arylation of carbonyl compounds is an ongoing challenge in organic synthesis. The first formal γ-arylation of carbonyl compounds via radical relay cross-coupling of α-bromocarbonyl precursors with boronic acids in the presence of alkenes is reported. This directing-group-free protocol allows for the rapid and straightforward access to a wide range of γ-arylated esters, ketones, and amides under ambient conditions with excellent functional group tolerance.

Ruthenium-Catalyzed ortho/meta-Selective Dual C-H Bonds Functionalizations of Arenes.

The first example of transition-metal-catalyzed ortho/meta-selective dual C-H functionalizations of arenes in one reaction is described. In this transformation, ortho-C-H chlorination and meta-C-H sulfonation of 2-phenoxypyri(mi)dines were achieved simultaneously under catalysis by [Ru(p-cymene)Cl]. The other reactant, namely, an arylsulfonyl chloride, played the role of both a sulfonation and chlorination reagent.

Synthesis of m-Alkylphenols via a Ruthenium-Catalyzed C-H Bond Functionalization of Phenol Derivatives.

The first example of the synthesis of m-alkylphenols via a ruthenium-catalyzed C-H bond functionalization of phenol derivatives with sec/tert-alkyl bromides is reported. Mechanistic studies indicated that the m-C-H bond alkylation may involve a radical process and that a six-membered ruthenacycle complex was the active catalyst. Moreover, this approach can provide an expedited strategy for the atom-/step-economical synthesis of many noteworthy pharmaceuticals and other functional molecules.