A direct α‐Csp3‐H methylenation of 1,3‐diketones to afford methylene‐bridged bis‐1,3‐dicarbonyl derivatives using dimethyl sulfoxide (DMSO) as a one‐carbon source was achieved in moderate to high yields in the presence of Selectfluor. The 1,3‐diketones can also be efficiently converted into Hantzsch‐type pyridines via one‐pot three‐component annulation reaction in the presence of DMSO and ammonium salt. The procedure avoids the use of transition metal catalysts and the reaction is efficient and operationally convenient.

A direct methylenation of amides to afford methylene‐bridged bisamides mediated by Selectfluor in the presence of dimethyl sulfoxide (DMSO) was achieved. DMSO plays a dual role in this reaction, as both solvent and a methylene source. The developed protocol avoids the use of transition metal catalysts and the reaction is efficient, operationally convenient and tolerable in air and water.

An efficient one-pot four-component condensation and cyclization of ketones with DMF and ammonium acetate for the synthesis of 2,4-diarylsubstituted pyridines promoted by Selectfluor has been achieved. Symmetrical pyridines were obtained selectively when non-methyl ketones were used as the starting materials. Two CÀ C and CÀ N bonds are formed during the oxidative cyclization process.[a] J.

An efficient method for the synthesis of 3-functionalized quinolines from acetophenones and anthranil mediated by Selectfluor was achieved.