Ru(ii)-Pheox-catalyzed Si–H insertion reaction: construction of enantioenriched carbon and silicon centers

Abstract

We established a highly enantioselective Si-H insertion reaction to construct chiral centers at the carbon and silicon atoms, using a Ru(ii)-pheox catalyst. The catalytic asymmetric Si-H insertion reaction of α-methyl-α-diazoesters proceeded smoothly with excellent stereoinduction at both the neighboring carbon and silicon atoms (up to 99% yield and 99% ee).

Computational chemical analysis of Ru(II)‐Pheox–catalyzed highly enantioselective intramolecular cyclopropanation reactions

“…Ru(II)‐Pheox can be easily synthesized from a commercially available benzoic acid derivative, an amino alcohol and a Ru source, and effectively promotes enantioselective intermolecular and intramolecular cyclopropanations with electron‐rich olefins, as well as electron‐deficient olefins, under mild reaction conditions. Moreover, we have reported Ru(II)‐Pheox–catalyzed highly enantioselective carbene insertion reactions into sp 3 Si–H single bonds . These results suggested that our catalytic system could also be applied to carbene transfer reactions for σ‐bond formation with high enantioselectivities and yields.…”

“…Moreover, we have reported Ru(II)-Pheox-catalyzed highly enantioselective carbene insertion reactions into sp 3 Si-H single bonds. 18 These results suggested that our catalytic system could also be applied to carbene transfer reactions for σ-bond formation with high enantioselectivities and yields. However, to date, the asymmetric induction mechanism in carbene transfer reactions catalyzed by the Ru(II)-Pheox complex has not been clarified.…”

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

“…The first example of an enantioselective insertion reaction of amethyl-substituted a-diazoesters into the Si-H bond using Ru as catalyst was reported by Chanthamath and Iwasa. 52 Using chiral Ru II -pheox catalyst, they produced a wide range of a-silylesters with high yields and moderate to good enantioselectivities (Scheme 41). They also showed that other silane sources exhibit much higher activities and enantioselectivities than PhMe2SiH (Scheme 42).…”

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

“…14 This reaction was rst described by Kramer and Wright in 1963. 15 Since then, pivotal breakthroughs have been made with Ru-, 16 Rh-, 17 Ir-, 18 Ag-, 19 Cu-, 20 and enzyme-catalysed 21 insertion reactions of diazo compounds into the Si-H bond. Iron catalysis being one of our group's major areas of research, 22 we developed a highly efficient iron-catalysed insertion reaction of a-diazoesters into Si-H bonds.…”