Site-Selective Linear Alkylation of Anilides by Cooperative Nickel/Aluminum Catalysis.

We report meta- and para-selective linear alkylation reactions of anilides with alkenes by nickel/N-heterocyclic carbene (NHC) and aluminum catalysis. With a less bulky NHC, the alkylation reaction of N-methyl-N-phenylcyclohexanecarboxamides proceeded mainly at the meta position. In contrast, a bulky NHC ligand led to the para-selective alkylation of N-sec-alkyl anilides.

para-Selective Alkylation of Benzamides and Aromatic Ketones by Cooperative Nickel/Aluminum Catalysis.

We report a method that ensures the selective alkylation of benzamides and aromatic ketones at the para-position via cooperative nickel/aluminum catalysis. Using a bulky catalyst/cocatalyst system allows reactions between benzamides and alkenes to afford the corresponding para-alkylated products. The origin of the high para-selectivity has also been investigated by density functional theory calculations.

para-Selective Alkylation of Sulfonylarenes by Cooperative Nickel/Aluminum Catalysis.

A method for the para-selective alkylation of a variety of arenesulfonamides and aromatic sulfones with 1-alkenes by cooperative nickel/aluminum catalysis has been developed. Taking advantage of the sulfornyl functionality serving as a removable ortho-directing group, the reaction can be applied to facile access to 1,3-dialkyl-substitued benzenes.