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The carbonylation of alkenes is tremendously important industrial process, but many substrates are highly challenging. Here the authors report a highly active catalytic system for the alkoxycarbonylation of alkenes that is also general across the range of alkene substitution patterns.

The conversion of alkenes to esters is performed on a large scale worldwide, but relies on the use of toxic and flammable carbon monoxide. Here, the authors show a catalytic system where carbon dioxide—normally unreactive, but cheap and abundant—can be employed instead.

Conversion of one-carbon feedstocks to more complex structures is vital for the production of bulk chemicals. Here, the authors report a highly selective method for the conversion of carbon monoxide to ethylene glycol by means of an oxamide intermediate.

Liquid (organic) hydrogen carriers form a toolbox for the storage and transport of green hydrogen but organic salts have been scarcely investigated. Here, the authors present a potassium formate/potassium bicarbonate hydrogen storage and release energy system, that is applicable and shows stability over months.

Using CO2 as C1-feedstock for the chemical industry has attracted great attention. Here the authors develop a two-step cascade process to perform catalytic carbonylations of olefins, alkynes, and aryl halides using CO₂ and H₂.

The selective formation of Markovnikov products in carbonylation reactions is a challenging problem, especially from unactivated substrates. Now, a highly Markovnikov-selective alkoxycarbonylation reaction is described using a catalyst system based on palladium and the cataCXium ligand POMeCy(Ph). The resulting branched carboxylates are important structural components in many flavour and fragrance products.

The selective synthesis of non-symmetrical diamides and amido-esters is a challenge. Now a Pd-catalysed dicarbonylation method is reported that generates non-symmetrical diamides and amido-esters through diamino- and amino-alkoxy carbonylations of propargylic acetates using two different nucleophiles. Mechanistic studies reveal that the process occurs through a sequential carbonylation process.

Hydrogen carriers play an important role in the hydrogen economy. Now, methyl formate is proposed as a suitable chemical hydrogen source for a carbon-neutral hydrogen energy cycle, and faster catalytic hydrogen production rates are achieved compared with those from the widely investigated formic acid and methanol.

Carbon dioxide is an abundant and easily available source of carbon, produced as a waste product in large quantities worldwide. Here, the authors review recent work on activating and reacting carbon dioxide for use as a building block in organic synthesis.