Catalytic Functionalization of Methyl Group on Silicon: Iridium-Catalyzed C(sp³)–H Borylation of Methylchlorosilanes

Abstract

A methyl group of methylchlorosilanes undergoes C-H borylation in an iridium-catalyzed reaction with bis(pinacolato)diboron in cyclohexane at 80 °C, giving (borylmethyl)chlorosilanes selectively.

Theoretical and Computational Study of a Complex System Consisting of Transition Metal Element(s): How to Understand and Predict Its Geometry, Bonding Nature, Molecular Property, and Reaction Behavior

“…Another important reason is that diborane is very reactive and thereby the oxidative addition of diborane easily occurs to the iridium(I) boryl species to afford the iridium(III) triboryl complex, indicating that the iridium(I) boryl complex cannot exist as a stable species under the catalytic reaction conditions. Actually, This type of CH σ-bond activation followed by borylation with diborane is an attractive catalytic reaction and many reports have been presented to date 108,109,115,116 because the C H bond activation and the functionalization are achieved at one time. One important development of this reaction is the extension to the borylation of a C(sp 3 )H bond.…”

“…This reaction was shown to be facile in the recently reported Ir-catalyzed C(sp 3 ) H borylation of chlorosilane. 116 A recent DFT study reported that the reaction occurs via oxidative addition of the C(sp 3 )H bond to the iridium(III) triboryl complex followed by the reductive elimination of borylated product, 117 which is essentially the same as the mechanism of Ir-catalyzed borylation of benzene. Also, the C(sp Another important development is to achieve regioselective CH σ-bond activation in these direct borylation reactions, which is also an important target in the chemistry of CH activation because regioselective CH σ-bond activation is not easy.…”

3‐Silylated Cyclohexa‐1,4‐dienes as Precursors for Gaseous Hydrosilanes: The B(C6F5)3‐Catalyzed Transfer Hydrosilylation of Alkenes

“…Complete conversion of 4 into iPr 3 SiH and benzene by B(C 6 F 5 ) 3 was however observed. As the trimethylsilyl group is not easily functionalized, [14] we included precursor 5 with a phenyl-substituted silicon atom into our survey. That would later allow for oxidative degradation of the C À Si bond.…”

3‐Silylierte Cyclohexa‐1,4‐diene als Vorstufen für gasförmige Hydrosilane: die B(C6F5)3‐katalysierte Transferhydrosilylierung von Alkenen

“…Die vollständige Überführung von 4 in iPr 3 SiH und Benzol durch B(C 6 F 5 ) 3 wurde dennoch beobachtet. Da die Funktionalisierung der Trimethylsilylgruppe schwierig ist, [14] bezogen wir die Vorstufe 5 mit einem phenylsubstituierten Siliciumatom mit in unsere Untersuchung ein. Das bçte später die Mçglichkeit zum oxidativen Abbau der C-Si-Bindung.…”