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.