NHC-catalyzed Truce-Smiles rearrangement of N-aryl methacrylamides for the synthesis of trans-cinnamides.

Herein we describe a NHC-catalyzed Truce-Smiles rearrangement of N-aryl methacrylamides which enables the cleavage of an inert aryl C-N bond. A range of trans-cinnamides could be obtained by the direct construction of a C(aryl)-C(alkenyl) bond and functional groups such as Br, Cl, CN, and pyridinyl are compatible with NHC catalysis. The reaction features high atom-economy, transition-metal free catalysis, and easily available substrates.

Selective cine-arylation of tert-cyclobutanols with indoles enabled by nickel catalysis.

In previous literature, tert-cyclobutanols are widely studied for C-C bond activation exclusively leading to the formation of ordinary γ-substituted ketones. Herein, we first report a nickel-catalyzed cine-arylation of tert-cyclobutanols with indoles to access ß-aryl ketones with an unusual site-selectivity at the C3-position of tert-cyclobutanols. The reaction features earth-abundant nickel catalysis, excellent regioselectivity, high atom-economy, and broad substrate scope.