Selective reduction of carbon dioxide to bis(silyl)acetal catalyzed by a PBP-supported nickel complex

Ríos, Pablo; Curado, Natalia; López‐Serrano, Joaquín; Rodríguez, Amor

doi:10.1039/c5cc09650b

Cited by 94 publications

(58 citation statements)

References 37 publications

(3 reference statements)

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“…[1][2][3] A variety of catalysts have been discovered and developed for this reaction, including complexes of Co, 4 Cu, [5][6][7][8] Ir, [9][10][11][12][13][14] Ni, [15][16][17] Pd/Pt, 18 Rh, 19 Ru, [20][21][22][23][24][25] Sc, 26 Zn, [27][28][29] and Zr, 30 frustrated Lewis pairs, [31][32][33][34][35][36] organocatalysts, [37][38][39][40][41][42] alkali metal carbonates, 43 and even polar solvents such as DMF. 38 These reactions result in various reduction products including silyl-formates, -acetals, andethers, CO, and methane.…”

Section: Introductionmentioning

confidence: 99%

Reduction of carbon dioxide and organic carbonyls by hydrosilanes catalysed by the perrhenate anion

Morris

Weetman

Wennmacher

et al. 2017

Catal. Sci. Technol.

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aThe simple perrhenate salt [NĲhexyl) 4 ]ĳ(ReO 4 )] acts as a catalyst for the reduction of organic carbonyls and carbon dioxide by primary and secondary hydrosilanes. In the case of CO 2 , this results in the formation of methanol equivalents via silylformate and silylacetal intermediates. Furthermore, the addition of alkylamines to the reaction mixture favours catalytic amine N-methylation over methanol production under certain conditions. DFT analysis of the mechanism of CO 2 reduction shows that the perrhenate anion activates the silylhydride forming a hypervalent silicate transition state such that the CO 2 can directly cleave a Si-H bond. IntroductionThe hydrosilylation of CO 2 to silylformates and silylethers is an attractive route for CO 2 utilisation as, unlike hydrogenation, this reaction is exergonic due to the comparative ease of Si-H bond activation and the strength of the Si-O bond, and the availability of relatively inexpensive and environmentally benign hydrosilanes. 66 Important to this chemistry is the formation of a lipophilic ion pair in which electrostatic and hydrogen-bonding interactions are enhanced in the hydrophobic phase. This catalyst has the advantages of ease of synthesis and manipulation and lack of air-sensitivity, and the recovery of the precious metal is driven by straightforward reverse phase-transfer. Given the efficacy of this new catalyst system and the use of high oxidation state rhenium oxo complexes in reduction catalysis, it is shown here that perrhenate can act as a catalyst for the reduction of carbon dioxide to methanol equivalents by hydrosilanes, that the methylation of alkylamines using CO 2 as the C 1 source occurs under similar catalytic conditions, and that this method can be used to reduce aldehydes and ketones to silylalcohols. Results and discussion Reduction of carbon dioxideInitially, the reaction between CO 2 (2.5 bar), PhSiH 3 (2.0 mmol), and pyridinium perrhenate 1 (2.0 mol%) at 80°C in C 6 D 6 in a Teflon-tapped NMR tube was monitored by 1 H NMR spectroscopy. However, only 15% consumption of hydrosilane is seen under these conditions after 16 h ( Fig. S2 and S3, ESI †). In contrast, when the reaction is carried out using the simple lipophilic quaternary ammonium salt [NĲhexyl) 4 ]ĳReO 4 ] 2 (2.5 mol%) with PhSiH 3 in C 6 D 6 at 1 bar of

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Section: Introductionmentioning

confidence: 99%

Reduction of carbon dioxide and organic carbonyls by hydrosilanes catalysed by the perrhenate anion

Morris

Weetman

Wennmacher

et al. 2017

Catal. Sci. Technol.

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“…Under similar conditions, Serrano and Rodriguez evaluated a Nickel PBP-complex for the formation of bis(silyl) methylene acetal from CO2 in presence of Et3SiH with high selectivities (78->99%) and moderate to high conversion (41-91%) at 70°C. 17 Already in 2013, Berke and coworkers reported the hydrosilylation of CO2 using a Frustrated Lewis Pair (FLP) consisting for example of a rhenium hydride and B(C6F5)3 (Scheme 12) at 80°C. 21 Here the authors reported yields of ~90%.…”

Section: Scheme 12 Metal Catalysed Reduction Of Co2 With Et3sih Yielmentioning

confidence: 99%

Future perspectives for formaldehyde: pathways for reductive synthesis and energy storage

2017

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“…TES-promoted reactions that involve metal catalysts (Pd, Mo, Ni, Au, Mn or Ru complexes) have been successfully used for the regioselective hydrogenation of olefins, [22][23][24] imines, [25] nitriles, [26] nitro derivatives [27] and carbonyl compounds. [28][29][30][31] Alternatively, TES mixed with a suitable Brønsted acid can be used under metal-catalyst-free conditions, [32][33][34][35] e.g., for the reductive cleavage of sulfides, [36] ethers, [37,38] hydroxides [39,40] and acetoxy groups. [41] A TES/trifluoroacetic acid (TFA) mixture can also be used as the reducing agent to yield unsaturated heterocycles.…”

Section: Introductionmentioning

confidence: 99%

Use of Triethylsilane for Directed Enantioselective Reduction of Olefines: Synthesis of Pyrazino[2,1‐c][1,4]oxazine‐6,9‐diones with Full Control of the Absolute Configuration

2018

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Herein, we report the use of triethylsilane for the synthesis of hexahydropyrazino[2,1‐c][1,4]oxazine‐6,9‐diones with full control of three stereocenters. Unsaturated tetrahydropyrazino‐oxazine‐diones were prepared in accordance with a previously reported procedure and were treated with triethylsilane‐trifluoroacetic acid. The stereoselectivity of the reduction was completely dependent on the overall conformation of the oxazine scaffold, which was a consequence of the C9 configuration of the starting material. The results prove that triethylsilane can be used for directed enantioselective syntheses of single or fused morpholine‐based heterocycles.

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Selective reduction of carbon dioxide to bis(silyl)acetal catalyzed by a PBP-supported nickel complex

Cited by 94 publications

References 37 publications

Reduction of carbon dioxide and organic carbonyls by hydrosilanes catalysed by the perrhenate anion

Reduction of carbon dioxide and organic carbonyls by hydrosilanes catalysed by the perrhenate anion

Future perspectives for formaldehyde: pathways for reductive synthesis and energy storage

Use of Triethylsilane for Directed Enantioselective Reduction of Olefines: Synthesis of Pyrazino[2,1‐c][1,4]oxazine‐6,9‐diones with Full Control of the Absolute Configuration

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