Contrary to the accepted convention, this work shows that Minisci-type C−H alkylation does not require any metal, photocatalyst, light, or prefunctionalization of the readily available and inexpensive carboxylic acids to proceed well under mild conditions. These mild conditions can be utilized for late-stage alkylations of complex molecules, including pharmaceutical compounds and light-sensitive compounds which degrade under photocatalytic conditions.

The enantioselective bromocyclization of allenes is accomplished through the use of a chiral dinuclear gold complex and/or chiral phosphate anions in the presence of an Nbromolactam as an electrophilic bromine source. This method provides access to heterocyclic vinyl bromides with an allylic stereocenter in excellent yield and enantioselectivity.These enantioenriched vinyl bromides may serve as a handle for further derivatization via cross-coupling reactions.

We report a silver-induced switching of regioselectivity in gold-catalyzed reactions, and we provide mechanistic evidence to suggest a true “silver effect”: that is, one that is implicated in the catalytic process itself, via σ-gold π-silver acetylides. These results are of significance because they clearly show that the use of silver as halide abstractors in gold-catalyzed reactions may result in “silver effects” when terminal alkyne substrates are involved.

Herein we report an efficient catalytic system for the titanium-promoted enantioselective addition of organolithium reagents to aldehydes, based on chiral Ar-BINMOL ligands. Unprecedented yields and enantioselectivities are achieved in the alkylation reactions of aliphatic aldehydes. Remarkably, methyl-

Reactions of heteroaromatic compounds with 3-methyl substituted 2-quinonyl boronic acids proceeded by 1,4-addition followed by spontaneous protodeboronation, leading directly to the Friedel-Crafts alkylation products instead of the commonly observed alkenylation derivatives resulting from quinones. The boronic acid acts as a temporary regiocontroller, making the system a highly reactive quinone equivalent and opening a direct access to 5,5-disubstituted cyclohexene-1,4-diones.