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Cobalt-Driven Cross-Dehydrocoupling of Silanes and Amines for Silylamine Synthesis
Ewelina Szafoni ; Krzysztof Kuciński ; Grzegorz Hreczycho ChemCatChem,e202400143. DOI: 10.1002/cctc.202400143
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Abstract: Cobalt complexes featuring triazine-based PNP ligands have proven to be exceptionally active and chemoselective pre-catalysts in facilitating the dehydrogenative coupling between silanes and amines, leading to the synthesis of diverse aminosilanes. Notably, even challenging substrates exhibited high reactivity. The catalyst‘s unique feature of avoiding coupling with tertiary silanes enhances process chemoselectivity. It facilitates a more precise synthesis of silylamines possessing of SiH2?N and SiH?N motifs, overcoming challenges associated with broader reactivity seen in previous systems. In terms of its remarkable chemoselectivity, it is also noteworthy that the catalytic system exhibits both versatility and efficacy in converting substrates with untouched double and triple carbon-carbon bonds. This accomplishment is particularly significant, given previous challenges brought about by the activity of commonly employed catalysts in the competitive hydrosilylation process.
CAS No. : | 775-12-2 | MDL No. : | MFCD00003002 |
Formula : | C12H12Si | Boiling Point : | - |
Linear Structure Formula : | SiH2(C6H5)2 | InChI Key : | BPYFPNZHLXDIGA-UHFFFAOYSA-N |
M.W : | 184.31 | Pubchem ID : | 6327659 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280 | UN#: | N/A |
Hazard Statements: | H315 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With potassium hexamethylsilazane; In neat liquid; at 30℃; for 2h;Schlenk technique; Inert atmosphere; | General procedure: Catalyzed CDC reactions were carried out using the following standard protocol. In the glove box, the chosen pre-catalyst (0.05 mmol) was loaded into a Schlenk tube, and subsequently the alcohol (n x 0.05 mmol, n equiv.) followed by silane (n' x 0 0.05 mmol, n' equiv.) were added. The reaction mixture was stirred at the desired temperature (30C), which was controlled by an oil bath. After the required period, the reaction was quenched by adding CDCl3 to the mixture. Substrate conversion was monitored by examination of the 1H NMR spectrum of the reaction mixture and comparing relative intensities of resonance characteristics of the substrates and products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | General procedure: A typical procedure (Table 2, entry 1) is as follows. To a stirredsolution of Ni(acac)2 (1a) (1.3 mg, 0.005 mmol) in THF (5 mL) wasadded 1-octene (112 mg, 1.0 mmol) and (EtO)3SiH (164 mg,1.0 mmol) at room temperature. After the mixture was stirred for1 min, NaBHEt3 (1.0Min THF, 5 mL, 0.005 mmol) was added and theresulting mixture was heated at 50 C. The solution was stirred atthe same temperature, and the progress of the reaction wasmonitored by GLC. After completion of the reaction, mesitylene(60 mg, 0.50 mmol) was added as an internal standard to the reactionmixture. The GLC analysis of the resulting solution revealedthe formation of (EtO)3(nOct)Si (0.90 mmol, 90%) and (EtO)4Si(0.05 mmol, 5%). The solutionwas concentrated under vacuum, andthe residue was purified by gel permeation chromatography (GPC)using toluene as an eluent to give (EtO)3(nOct)Si (234 mg,0.85 mmol, 85%). The 1H, 13C{1H} and 29Si{1H} NMR spectra of theisolated compound are consistent with the reported data. A similarprocedurewas employed for the hydrosilylation using other silanesand 1,3-diene/alkenes/alkynes. These reactions were carried out atroom temperature except for the reactions, Table 2, entries 2-3.The 1H/13C NMR spectroscopic data for the new compounds aregiven in the supplementary data. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With C21H41N3NiP2; In N,N-dimethyl-formamide; at 20 - 60℃; for 36h;Sealed tube; | General procedure: [0182] Using tertiary amines, such as Et3N and DABCO (1,4-Diazabicyclo[2.2.2]octane) and imine, such as DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) as the catalysts led to no methanol product (Table 3, entries 4-6). The reaction worked well in polar aprotic solvents such as DMF, THF, and MeCN, with slower reaction rates in THF and MeCN (Table 3, entries 7 and 8), presumably because DIVIF can act as a Lewis base to help to activate silane and thus accelerate the reaction.28 No reaction was observed in CH2C12 and toluene (Table 3, entries 9 and 10). Further screening of catalyst loadings (Table 3, entries 11-16) revealed that diphenylsilane could be fully consumed with a catalyst loading as low as 0.02 mol% (Table 3, entry 16). The turnover number (TON) and turnover frequency (TOF) for hydride 2 as the catalyst in this reaction could reach 4900 and 136 h?, respectively (Table 3, entry 16), much higher than those of the (N-heterocyclic carbene) NHC catalysts.?4 To the best of our knowledge, this is the highest TON and TOF reported for the reduction of CO2 with silane to methanol.[0188] General procedures for reduction of CO2 to methanol: to a fresh vial was added nickel PN3P-pincer complex 2 (4.6 mg, 0.01 mmol), and 1.8 mL of DIVIF was introduced. The vial was sealed, and CO2 was introduced into the vial via a balloon. The reaction was allowed to stir for 30 mm at room temperature, after which diphenylsilane (0.19 mL, 1 mmol) was introduced. The reaction was quenched after 18 h by adding 2 equivalents of NaOH/H20 solution. It was stirred for another 24 h before an aliquot of isopropyl alcohol was added as an internal standard. An aliquot of 0.2 mL was removed from the sample and diluted with dichloromethane before the resulting mixture was subjected to GC analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1,10-Phenanthroline; zinc diacetate; In [D3]acetonitrile; at 80℃; under 1875.19 Torr; for 24h;Autoclave; Glovebox;Catalytic behavior; Kinetics; | Zn(OAc)2 (0.02mmol, 3.7 mg),phen (0.06mmol, 10.8 mg), CD3CN (1 mL), Ph2SiH2 (3mmol,552 mg) were added to an autoclave. The autoclave was sealedtightly, and filled with CO2 to 0.25MPa (initial pressure). After24 h reaction at 80 C, CO2 was released gently, and mesitylenewas added as an internal standard. The solution was then transferredto a J. Young NMR tube for NMR analysis. 1HNMR(400 MHz): 3.6 ppm for CH3OSiR3; 13C{1H}NMR (100 MHz):52 ppm for CH3OSiR3 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With [{(DIPP-nacnac)CaH(thf)}2]; In toluene; at 100℃; for 15h;Inert atmosphere; Schlenk technique; Sealed tube; | General procedure: In a nitrogen-filled glovebox, complex 1 (0.025 mmol), terminal alkyne (0.5 mmol)and silane (1.5 mmol) in toluene (2 mL) were loaded into a 25 mL Schlenk tube. Thistube was sealed, taken out of the glovebox, and put into an oil bath which had beenpreviously set to 100 oC. After completion of the reaction (monitored by 1H NMR), thereaction was quenched by opening to air, and the volatiles of the reaction mixture wereremoved under vacuum at room temperature. The residue was purified by columnchromatography on silica gel to provide alkynylsilane. |
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