We report herein a simple, metal- and additive-free, photoinduced borylation of haloarenes, including electron-rich fluoroarenes, as well as arylammonium salts directly to boronic acids. This borylation method has a broad scope and functional group tolerance. We show that it can be further extended to boronic esters, and carried out on gram scale as well as under flow conditions.
We report herein a simple, additive- and metal-free, photoinduced, dual C–H/C–X-borylation of chloro-, bromo-, and iodoarenes. The reaction produces 1,2- and 1,3-diborylarenes on gram scales under batch and continuous flow conditions. The regioselectivity of the dual C–H/C–X-borylation is determined by the solvent and the substituents in the parent haloarenes.
A one-step synthesis of 1,1′- and 2,2′-methylene-bridged N-heterobiaryls directly from the corresponding N-heterocycles in a reaction with methylmagnesium chloride in the presence of catalytic amounts of N,N,N′N′-tetramethylethylenediamine (TMEDA) under thermal and microwave conditions is reported. The split-and-merge methylenation of 2,2′-N-heterobiaryls and the direct ortho-alkylation of quinoline and isoquinoline with Grignard reagents have also been developed. Mechanistic studies identified several intermediates and provided insights into the formation and roles of magnesium hydride species in the process.
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