Fe-catalysed insertion reaction of α-diazocarbonyls into X-H bonds (X = Si, S, N, and O) in dimethyl carbonate as a suitable solvent alternative.

The insertion reaction of a broad range of diazo compounds into Si-H bonds was found to be efficiently catalysed by Fe(OTf) in an emerging green solvent dimethyl carbonate (DMC). The α-silylated products were obtained in good to excellent yields (up to 95%). Kinetic studies showed that the extrusion of N to form an iron carbene intermediate is rate-limiting.

α-Thiocarbonyl synthesis via the Fe-catalyzed insertion reaction of α-diazocarbonyls into S-H bonds.

Fe(OTf)2 was used to catalyze the insertion reaction of α-diazocarbonyls into S-H bonds at 40 °C. A wide range of α-thioesters were obtained in yields up to 96% within 24-48 h from their corresponding α-diazoesters. A variety of thiols were used for the unprecedented insertion reaction with an α-diazoketone, leading to yields up to 85% of α-thioketones.

Asymmetric Fe-Catalyzed Thia-Michael Addition Reaction to α,β-Unsaturated Oxazolidin-2-one Derivatives.

A highly enantioselective Fe-catalyzed thia-Michael addition to α,β-unsaturated carbonyl derivatives was developed. The scope of the reaction was demonstrated with a selection of aromatic, heterocyclic and aliphatic thiols, and various Michael acceptors. The corresponding β-thioethers were obtained in good to excellent yields (up to 98%) and moderate to excellent enantioselectivities (up to 96:4 er).

Iron-Catalyzed Carbene Insertion Reactions of α-Diazoesters into Si-H Bonds.

An efficient iron-catalyzed carbene insertion reaction of α-diazo carbonyl compounds into the Si-H bond was developed. A wide range of α-silylesters was obtained in high yields (up to 99%) from α-diazoesters using a simple iron(II) salt as catalyst.

Recent progress in the catalytic carbene insertion reactions into the silicon-hydrogen bond.

The following review will explore the historical development of Si-H bond insertion reactions, giving an up-to-date account on the metal catalysts often employed, in addition to an assessment of their strengths and weaknesses. Diazo compounds have great synthetic potential as versatile reagents for the formation of metal carbenes, allowing the selective formation of C-C and C-heteroatom bonds and thus the introduction of functional groups into organic molecules. C-Si bond-forming methods, that introduce silicon motifs into organic molecules, rely on catalysts derived from metals such as rhodium, copper, iridium, silver, ruthenium, and iron to achieve the desired activities and selectivities.

Copper-Catalyzed Carbenoid Insertion Reactions of α-Diazoesters and α-Diazoketones into Si-H and S-H Bonds.

An efficient copper-catalyzed carbenoid insertion reaction of α-diazo carbonyl compounds into Si-H and S-H bonds was developed. A wide range of α-silylesters and α-thioesters was obtained in high yields (up to 98%) from α-diazoesters using 5 mol% of a simple copper(I) salt as catalyst. Using 0.