On a direct course to the aldehyde: Hydrosilylation catalyzed by a well‐defined N‐heterocyclic‐carbene–iron complex under UV irradiation enabled the selective reduction of esters to aldehydes (see scheme; Bn=benzyl, Mes=mesityl). The low catalyst loading and very mild reaction conditions make this chemoselective transformation a promising alternative to the reduction of esters with diisobutylaluminum hydride.

The new routes and strategies for the synthesis of valuable 4(3H)-quinazolinones have been summarized.

Hydroesterification reactions represent a fundamental type of carbonylation reaction and constitute one of the most important industrial applications of homogeneous catalysis. Over the past 70 years, numerous catalyst systems have been developed that allow for highly linear-selective (anti-Markovnikov) reactions and are used in industry to produce linear carboxylates starting from olefins. In contrast, a general catalyst system for Markovnikov-selective alkoxycarbonylation of aliphatic olefins remains unknown. In this paper, we show that a specific palladium catalyst system consisting of PdX/N-phenylpyrrole phosphine (X, halide) catalyses the alkoxycarbonylation of various alkenes to give the branched esters in high selectivity (branched selectivity up to 91%). The observed (and unexpected) selectivity has been rationalized by density functional theory computation that includes a dispersion correction.