Transition metal catalysts are formidable tools towards greener chemistry, allowing for low-waste, energy-efficient, and selective reactions. And transition metal-catalysed carbonylation procedures are powerful methodologies for producing carbonyl-containing compounds. The existing reviews/chapters/books are mainly focused on noble metal (Ru, Rh, Ir, Pd, Pt) catalysed carbonylation reactions. In this review, achievements on non-noble metal (Mn, Fe, Cu, Co, Ni) catalysed carbonylative transformations have been summarized and discussed.

Dedicated to Paul Kamer, a great scientist and inspiring person. A series of hydroxy-functionalized phosphonium salts were studied as bifunctional catalysts for the conversion of CO 2 with epoxides under mild and solvent-free conditions. The reaction in the presence of a phenol-based phosphonium iodide proceeded via a first order rection kinetic with respect to the substrate. Notably, in contrast to the aliphatic analogue, the phenol-based catalyst showed no product inhibition. The temperature dependence of the reaction rate was investigated, and the activation energy for the model reaction was determined from an Arrhenius-plot (E a = 39.6 kJ mol À 1). The substrate scope was also evaluated. Under the optimized reaction conditions, 20 terminal epoxides were converted at room temperature to the corresponding cyclic carbonates, which were isolated in yields up to 99 %. The reaction is easily scalable and was performed on a scale up to 50 g substrate. Moreover, this method was applied in the synthesis of the antitussive agent dropropizine starting from epichlorohydrin and phenylpiperazine. Furthermore, DFT calculations were performed to rationalize the mechanism and the high efficiency of the phenol-based phosphonium iodide catalyst. The calculation confirmed the activation of the epoxide via hydrogen bonding for the iodide salt, which facilitates the ring-opening step. Notably, the effective Gibbs energy barrier regarding this step is 97 kJ mol À 1 for the bromide and 72 kJ mol À 1 for the iodide salt, which explains the difference in activity.

Deuterium labeled compounds find widespread application in life science. Herein, the deuteration of electron-rich (hetero)aromatic compounds employing B(CF) as the catalyst and DO as the deuterium source is reported. This protocol is highly efficient, simply manipulated, and successfully applied in the deuteration of 23 substrates including natural neurotransmitter-like melatonin. It is assumed that the weakening of the O-D bond ultimately results in the formation of electrophilic D.

Carbon dioxide (CO), a key greenhouse gas produced from both anthropogenic and natural sources, has been recently considered to be an important C1 building-block for the synthesis of many industrial fuels and chemicals. Catalytic hydrogenation of CO using a homogeneous system is regarded as an efficient process for CO valorization. This approach leads to the direct products including formic acid (HCOOH), carbon monoxide (CO), methanol (MeOH), and methane (CH). The hydrogenation of CO to CO followed by alkene carbonylation provides value-added compounds, which also avoids the tedious separation and transportation of toxic CO. Moreover, the reduction of CO with H in the presence of amines is of significance to attain fine chemicals through catalytic formylation and methylation reactions. The synthesis of higher alcohols and dialkoxymethane from CO and H has been demonstrated recently, which opens access to new molecular structures using CO as an important C1 source.

Herein, we report a detailed investigation of alkali and alkaline earth metal salts in combination with polyethers as catalytic systems for the synthesis of cyclic carbonates from epoxides and CO2. CaI2 showed superior activity compared to various other tested alkali and alkaline earth metal salts. Interestingly, in contrast to other catalytic protocols, the presence of hydroxyl groups hampered the reaction. Thus, poly­(ethylene glycol) dimethyl ethers (PEG DME) proved to be the most suitable polymer complexing agents. This catalytic protocol is based on a nontoxic and abundant metal as well as readily available polymer coordination agents. Notably, 26 terminal epoxides were converted even at room temperature with CO2 to the corresponding cyclic carbonates in yields up to 99%. Additionally, this system was also effective for the synthesis of 21 challenging internal carbonates based on fossil and renewable feedstock in yields up to 98%. Significantly, at a large scale, namely, 10 g of epoxide, a quantitative yield of cyclic carbonate was isolated in the presence of only 1 mol % catalyst under ambient conditions. Two different recycling strategies were tested which allowed the reuse of the catalyst up to 7 times without the loss of activity.

State-of-the-art Pd-catalyzed alkoxycarbonylation: catalyst development and applications.

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The rise of CO2 in atmosphere is considered as the major reason for global warming. Therefore, CO2 utilization has attracted more and more attention. Among those, using CO2 as C1-feedstock for the chemical industry provides a solution. Here we show a two-step cascade process to perform catalytic carbonylations of olefins, alkynes, and aryl halides utilizing CO2 and H2. For the first step, a novel heterogeneous copper 10Cu@SiO2-PHM catalyst exhibits high selectivity (≥98%) and decent conversion (27%) in generating CO from reducing CO2 with H2. The generated CO is directly utilized without further purification in industrially important carbonylation reactions: hydroformylation, alkoxycarbonylation, and aminocarbonylation. Notably, various aldehydes, (unsaturated) esters and amides are obtained in high yields and chemo-/regio-selectivities at low temperature under ambient pressure. Our approach is of interest for continuous syntheses in drug discovery and organic synthesis to produce building blocks on reasonable scale utilizing CO2.