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

Abstract

The insertion reaction of a broad range of diazo compounds into Si–H bonds was found to be efficiently catalysed by Fe(OTf)2 in an emerging green solvent i.e. dimethyl carbonate (DMC).

Recent Advances in Iron‐Catalyzed Chemical and Enzymatic Carbene‐Transfer Reactions

“…dimethyl carbonate (DMC) (Scheme 19). [39] After the optimization of the reaction conditions, different diazo compounds and silane moieties were explored to extend the substrate scope. It was seen that among the tested diazo compounds the higher yields were obtained for diazo compounds having electron‐withdrawing groups either on the para‐ or ortho ‐position of aryl moiety.…”

“…In addition of other carbene insertion reactions, Ollevier and group members studied the Fe(OTf) 2 catalyzed insertion of aliphatic and aromatic amines (83) into methyl α‐phenyl‐α‐diazoacetate (21) (Scheme 28). [39] They observed that primary aromatic amines gave high yield of desired products with no side reactions, however, reaction required prolonged time to get complete in case of secondary aromatic amines.…”

“… Fe(OTf) 2 catalyzed N−H insertion reactions of various amines with diazo compounds as carbene precursor [39] …”

The Power of Iron Catalysis in Diazo Chemistry

“…Next, the Ollevier group continued their study on iron-catalyzed Si-H insertions while opting for a greener solvent alternative to replace the commonly required dichloromethane (DCM). 29 They found that dimethyl carbonate (DMC) could be used for an Fe(OTf) 2 -catalyzed insertion reaction of -diazo compounds which proceeds in high yields (up to 98%) for a wide scope of diazo compounds and silanes. The reaction mechanism of this iron-catalyzed Si-H insertion was further examined.…”

“…Also, the Ollevier group reported Fe(OTf) 2 -mediated mono N-H insertions of methyl -diazo--phenylacetate with various primary and secondary amines. 29…”