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

Abstract

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.

Iron catalysts with N-ligands for carbene transfer of diazo reagents

“…by the metal-catalyzed carbene insertion into C-H and X-H functionalities, respectively. Since the first example of the copper-catalyzed O-H insertion by diazoketones reported in the 1950s, 147 the diazo-based carbene transfer into C-H and X-H bonds has been widely investigated and reviewed 3,5,6,[148][149][150][151][152][153][154] highlighting dirhodium(II) complexes as the most efficient catalysts, particularly for promoting C-H activations.…”

Boron‐Catalyzed C−C Functionalization of Allyl Alcohols

“…[18][19][20][21][22][23][24] In this respect, organic diazo reagents have had a profound influence as the carbene precursors. Their ability to insert between CÀH and heteroatom-H bonds is well documented.…”

“…Their ability to insert between CÀH and heteroatom-H bonds is well documented. [18][19][20][21][22][23][24] In this respect, organic diazo reagents have had a profound influence as the carbene precursors. [25] However, the utility of these reagents is underrepresented in non-transition metal catalysis.…”

Recent advances in Cu-catalyzed C(sp3)–Si and C(sp3)–B bond formation

“…In furthering Zhou's initial report [76], Ollevier and co-workers [77] recently described carbene insertions, starting with 229, into Si-H bonds, leading to a wide variety of silylated products [18]. The original work by Zhou included asymmetric carbenoid insertions using spiro-bisimine ligand L25 at cryogenic temperatures (Scheme 39A).…”

“…Many recent reviews already cover the syntheses and applications of organosilicon [17][18][19][20] and organoboron [21][22][23][24] com-Scheme 1: Pharmaceuticals possessing a silicon or boron atom.…”