Rhodium-Catalyzed, Efficient Deutero- and Tritiosilylation of Carbonyl Compounds from Hydrosilanes and Deuterium or Tritium

Rubio, M.; Campos, Jesús; Carmona, Ernesto

doi:10.1021/ol202117t

Cited by 27 publications

(9 citation statements)

References 26 publications

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“…Synthesis of C according to the Following Procedure. 42 The target compound was obtained according to General Procedure with triethylsilane (23.2 mg, 0.2 mmol), and HFIP was replaced by toluene. The crude product was purified by silica gel chromatography using petroleum ether as an eluent to give pure product C (49 mg, 76% yield) as a colorless oil.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Chemoselective Hydrosilylation of the α,β-Site Double Bond in α,β- and α,β,γ,δ-Unsaturated Ketones Catalyzed by Macrosteric Borane Promoted by Hexafluoro-2-propanol

et al. 2020

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The B(C6F5)3-catalyzed chemoselective hydrosilylation of α,β- and α,β,γ,δ-unsaturated ketones into the corresponding non-symmetric ketones in mild reaction conditions is developed. Nearly 55 substrates including those bearing reducible functional groups such as alkynyl, alkenyl, cyano, and aromatic heterocycles are chemoselectively hydrosilylated in good to excellent yields. Isotope-labeling studies revealed that hexafluoro-2-propanol also served as a hydrogen source in the process.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Chemoselective Hydrosilylation of the α,β-Site Double Bond in α,β- and α,β,γ,δ-Unsaturated Ketones Catalyzed by Macrosteric Borane Promoted by Hexafluoro-2-propanol

et al. 2020

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“…The resulting solution was charged in a J-Young NMR tube. The catalytic reaction was monitored by 1 H NMR spectroscopy for the appropriate time leading to the formation of the corresponding reduction products, which were identified by comparison of the 1 H NMR data with those in the literature. ,,− Except for cyclohexanone and 4′-cyanoacetophenone hydrosilylation reactions, GC-MS analysis of all crude products was also performed and further confirmed 1 H NMR analysis. GC-MS data: acetophenone hydrosilylation , t R = 4.60 min, m / z 217.4 (M + -29(Et), Calcd for C 10 H 25 OSi 2 + : 217.1, Et 3 SiOSiEt 3 ); t R = 5.28 min, m / z 207.3 (M + -29(Et), Calcd for C 12 H 19 OSi + : 207.1, 12 ); t R = 5.85 min, m / z 211.1 (M + -15(Me), Calcd for C 15 H 15 O + : 211.1, 13 ).…”

Section: Methodsmentioning

confidence: 87%

Robust Two-Coordinate Zn(II) Organocations Supported by Bulky-Yet-Flexible IPr* Carbene: Synthesis, Structure, and Distinct Reactivity in Hydrosilylation Catalysis

Xu,

Gourlaouen,

Jacques

et al. 2023

Organometallics

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The present study details the synthesis and characterization of novel Zn(II)-based organocations of the type [IPr*-Zn-R]+ (IPr* = 1,3-bis[2,6-bis(diphenylmethyl)-4-methylphenyl]-1,3-dihydro-2H-imidazol-2-ylidene; R = alkyl, aryl) and their use in styrene, alkyne, and carbonyl hydrosilylation catalysis. The neutral IPr* adducts [IPr*-ZnR2] (1, R = Me; 2, R = Et; 3, R = Ph) were prepared by the reaction of IPr* with an equimolar amount of ZnR2 and isolated in good yields. Despite the severe steric hindrance of IPr*, compounds 1–3 are robust in solution, reflecting the bulky-yet-flexible nature of carbene IPr*. Adducts 1 and 2 can be readily ionized by [Ph3C][B(C6F5)4] to produce two-coordinate Zn(II) cations [IPr*-ZnMe]+ ([4]+) and [IPr*-ZnEt]+ ([5]+), both isolated in high yields (>85%) as [B(C6F5)4]− salts. Interestingly, the more Lewis acidic cation [IPr*-ZnC6F5]+ ([6]+), prepared by reaction of [4][B(C6F5) 4 ] with a B(C6F5)3/HSiEt3 mixture, is further stabilized through π arene interactions with Zn(II), indicating that IPr* may provide steric and electronic stabilization to Zn(II). The latter certainly explains the improved hydrolytic stability of the salt [6][B(C6F5)4]. Zn cations of the [IPr*-ZnR]+ series are less Lewis acidic than their [IPr-ZnR]+, yet they display a distinct reactivity in hydrosilylation catalysis. Thus, cation [6]+ catalyzes at room-temperature styrene and alkyne hydrosilylation with HSiEt3 as the silane source. Remarkably, it is also a highly effective ketone/aldehyde hydrosilylation catalysis for a rather broad silane and ketone scope and performs much better than [IPr-ZnR]+ systems. The density functional theory (DFT)-estimated mechanism for the hydrosilylation of benzophenone by [6]+ suggests that Si–H activation by the cationic Zn(II) center is required for the catalysis to proceed. Overall, the improved hydrolytic stability and straightforward synthesis of a well-defined Zn-based Lewis acid such as [6][B(C6F5)4] may promote its further use in various Lewis-acid-mediated transformations.

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“…The deutero product HN(SiMe 2 D) 2 was subsequently employed for a solid‐state 2 H NMR spectroscopy study of the molecular dynamics of the SiMe 2 D moiety grafted to various forms of silica 8. In 2010, Carmona and co‐workers reported a highly efficient rhodium‐catalyzed preparation of deuterated and even tritiated silanes under an atmosphere of D 2 or T 2 2b,9. It was possible to prepare Et 3 SiD, Me 2 PhSiD and Ph 2 SiD 2 on a scale of several grams with very low catalyst loading (for example: 0.01% catalyst in neat Et 3 SiH at 50 °C, 0.5 bar D 2 , >99% D incorporation) (Scheme ).…”

Section: Methodsmentioning

confidence: 99%

Silane Deuteration Catalyzed by Ruthenium Bis(dihydrogen) Complexes or Simple Metal Salts

et al. 2014

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The deuteration of a diverse group of silanes: alkyl-, aryl-, alkoxy-and chlorosilanes, siloxane and silazane, under an atmosphere of dideuterium (D 2 ) was explored with ruthenium bis(dihydrogen) dihydride complexes and hydrated metal salts. Deuterium incorporation of greater than 97% for the silanes OA C H T U N G T R E N N U N G (SiMe 2 H) 2 , Et 3 SiH, (EtO) 3 SiH and Me 2 ClSiH was possible with 0.

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Rhodium-Catalyzed, Efficient Deutero- and Tritiosilylation of Carbonyl Compounds from Hydrosilanes and Deuterium or Tritium

Cited by 27 publications

References 26 publications

Chemoselective Hydrosilylation of the α,β-Site Double Bond in α,β- and α,β,γ,δ-Unsaturated Ketones Catalyzed by Macrosteric Borane Promoted by Hexafluoro-2-propanol

Chemoselective Hydrosilylation of the α,β-Site Double Bond in α,β- and α,β,γ,δ-Unsaturated Ketones Catalyzed by Macrosteric Borane Promoted by Hexafluoro-2-propanol

Robust Two-Coordinate Zn(II) Organocations Supported by Bulky-Yet-Flexible IPr* Carbene: Synthesis, Structure, and Distinct Reactivity in Hydrosilylation Catalysis

Silane Deuteration Catalyzed by Ruthenium Bis(dihydrogen) Complexes or Simple Metal Salts

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