Highly stereoselective metathesis reaction between optically active hydrosilane and copper(I) salt in 1,3-dimethyl-2-imidazolidinone

Ito, Hajime; Ishizuka, Tomoko; Okumura, Tomoko; Yamanaka, Hiroshi; Tateiwa, Jun-ichi; Sonoda, Motohiro; Hosomi, Akíra

doi:10.1016/s0022-328x(98)00923-1

Cited by 23 publications

(14 citation statements)

References 14 publications

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“…All attempts led invariably back to structures corresponding to Cu(H)-(PH 3 ) 2 + SiH 2 Me 2 , in which the silane interacts very weakly with the copper complex. [17] The stabilization energy for these adducts is found to range between 2.2 and 3.5 kcal mol -1 , i.e., values which are even lower than that obtained for the adduct between Cu(H)(PH 3 ) 2 and O=CMe 2 .…”

Section: Theoretical Studiesmentioning

confidence: 81%

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Mechanistic Studies on the Copper‐Catalyzed Hydrosilylation of Ketones

et al. 2010

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The copper‐catalyzed asymmetric hydrosilylation of ketones is an efficient method for the synthesis of chiral enantiopure secondary alcohols. Herein, we present a detailed computational study (DFT/B3LYP) of the copper(I)‐catalyzed reaction. In particular, the two transition states involved in the catalytic cycle have been determined. The insertion of the ketone into the Cu–H bond was found to have a lower activation barrier than the reaction of the copper alkoxy intermediate with the silane, which regenerates Cu–H along with the silyl ether product. Our findings also reveal the importance of the copper hydride dimer in controlling the reactivity toward the ketone. The conclusions are supported by experimental mechanistic investigations including kinetic studies, kinetic isotope effect, and isotope labeling measurements.

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Section: Theoretical Studiesmentioning

confidence: 81%

“…The same is true for the results, not reported here, that were obtained for the two other models of the catalysts. [17] One finds some variations, but they do not exceed a few kcal mol -1 . In particular, the second step remains the most difficult step.…”

Section: Theoretical Studiesmentioning

confidence: 98%

Mechanistic Studies on the Copper‐Catalyzed Hydrosilylation of Ketones

et al. 2010

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“…As shown on Fig. 1, the formation of a r bond between the copper and hydrogen atom, occurs through transmetalation [18,17,30] passing by a 4 center transition state.…”

Section: Activation Of the Pre-catalystmentioning

confidence: 93%

“…A r-bond metathesis between the copper fluoride and the hydrosilylation reagent then expectedly generates the copper hydride species (Scheme 2) [30].…”

Section: Introductionmentioning

confidence: 99%

Mechanism of ketone hydrosilylation by Cu(I) catalysts: A theoretical study

Gathy¹,

Peeters²,

Leyssens³

2009

Journal of Organometallic Chemistry

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“…Based on the observed results, two plausible mechanisms can be proposed (Scheme 2): (i) an oxidative addition of the silane to the copper(I) hydride complex in order to generate a copperA C H T U N G T R E N N U N G (III) intermediate (path A) [14] or (ii) (BINAP)CuH may interact with one equivalent of silane to form a pentacoordinate silicon [15] intermediate species (BINAP)CuH 2 Si- A C H T U N G T R E N N U N G (HMePh), which would then be able to react with the ketone (path B). Further studies are required to fully understand the mechanistic pathway.…”

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confidence: 99%