Selective hydrosilylation of alkynes and ketones: contrasting reactivity between cationic 3-iminophosphine palladium and nickel complexes

Tafazolian, Hosein; Yoxtheimer, Robert; Thakuri, Rajendr S.; Schmidt, Joseph A. R.

doi:10.1039/c7dt00832e

Cited by 26 publications

(15 citation statements)

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“…Low yield was observed when using CHCl 3 or CH 2 Cl 2 along with significant formation of precipitate. Unsurprisingly, THF and ACN both did not work well, as we have previously observed poor efficiency with polar coordinating solvents[25a] in related hydroamination reactions. With benzene identified as the best solvent, an increase of HBpin from 1.0 to 1.2 equivalents dramatically increased the efficiency of the reaction, reducing reaction times and necessary catalyst loading (entry 7, Table ).…”

Section: Resultsmentioning

confidence: 91%

“…Cationic [(3IP)nickel(II)allyl] + pre‐catalyst 1 was synthesized using the previously published procedure from our lab. [25a] All substrates and solvents used for this catalysis were dried and degassed before transferring into the glove box. Deuterated chloroform and benzene (Cambridge Isotope Laboratories) were dried using calcium hydride and sodium metal, respectively, and degassed via three freeze‐pump‐thaw cycles.…”

Section: Methodsmentioning

confidence: 99%

“…Iminophosphine is a bidentate unsymmetrical ligand having both strong phosphine and weak imine donor groups (Figure ). These ligands have proven successful in several catalytic transformations with nickel . Herein we report the utility of our [(iminophosphine)nickel(allyl)] + ( 1 ) complex (Figure ) as an efficient catalyst for the hydroboration of aldehydes and N ‐allylimines.…”

Section: Introductionmentioning

confidence: 99%

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Nickel(II) Catalyzed Hydroboration: A Route to Selective Reduction of Aldehydes and N‐Allylimines

Hossain

Schmidt

2020

Eur J Inorg Chem

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A cationic [(iminophosphine)nickel(allyl)] + complex was found to be sufficiently electrophilic to activate aldehydes and N-allylimines to undergo hydroboration with pinacolborane (HBpin) under mild reaction conditions. The catalyst displayed excellent selectivity toward aldehydes in the presence of ketones. A wide variety of functional groups were tolerated, includ- [a] I. 1877 ing halogens, NO 2 , CN, OMe, and alkenes for both aldehydes and imines. Electron-rich substrates were found to be significantly more reactive than their electron poor counterparts, a feature that was correlated to their enhanced ability to coordinate to the Lewis acidic nickel center. [40] Colorless liquid (60 mg, 81 % isolated yield). 1 H NMR (600 MHz, CDCl 3 ): δ = 7. 33-7.30 (m, 4H), 7.25-7.22 (m, 1H), 5.92 (ddt, 3 J HH = 17.2, 3 J HH = 10.2, 3 J HH = 6.0 Hz, 1H), 5.19 (dq, 3 J HH = 17.2, 4 J HH = 2 J HH = 1.5 Hz, 1H), 5.10 (dq, 3 J HH = 10.2, 4 J HH = 2 J HH = 1.5 Hz, 1H), 3.78 (s, 2H), 3.27 (dt, 3 J HH = 6.0, 4 J HH = 1.5 Hz, 2H), 1.47 (br s, 1H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ): δ = 140. 3, 136.9, 128.5, 128.3, 127.1, 116.1, 53.4, 51.9. [30a] Colorless liquid (74 mg, 92 % isolated yield). 1 H NMR (600 MHz, CDCl 3 ): δ = 7.22 (d, 3 J HH = 7.9 Hz, 2H), 7.15 (d, 3 J HH = 7.9 Hz, 2H), 5.94 (ddt, 3 J HH = 17.2, 3 J HH = 10.2, 3 J HH = 6.0 Hz, 1H), 5.20 (dq, 3 J HH = 17.2, 4 J HH = 2 J HH = 1.6 Hz, 1H), 5.12 (dq, 3 J HH = 10.2, 4 J HH = 2 J HH = 1.6 Hz, 1H), 3.76 (s, 2H), 3.28 (dt, 3 J HH = 6.0, 4 J HH = 1.6 Hz, 2H), 2.35 (s, 3H), 1.52 (br s, [41] Colorless liquid (81 mg, 91 % isolated yield). 1 H NMR (600 MHz, CDCl 3 ): δ = 7.24 (d, 3 J HH = 8.3 Hz, 2H), 6.86 (d, 3 J HH = 8.3 Hz, 2H), 5.93 (ddt, 3 J HH = 17.3, 3 J HH = 10.4, 3 J HH = 6.0 Hz, 1H), 5.19 (dq, 3 J HH = 17.3, 4 J HH = 2 J HH = 1.6 Hz, 1H), 5.11 (dq, 3 J HH = 10.4, 4 J HH = 2 J HH = 1.6 Hz, 1H), 3.79 (s, 3H), 3.73 (s, 2H), 3.26 (dt, 3 J HH = 6.0, 4 J HH = 1.6 Hz, 2H), 1.45 (br s, 1H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ): δ = 158. 7, 136.9, 132.5, 129.5, 116.1, 113.8, 55.4, 52.8, 51.8. N-Benzylprop-2-en-1-amine (2b): N-(4-Methylbenzyl)prop-2-en-1-amine (2c): N-(4-Methoxybenzyl)prop-2-en-1-amine (2d): N-(4-N,N-Dimethylaminobenzyl)prop-2-en-1-amine(2e): [30a] Pale yellow liquid (87 mg, 91 % isolated yield). 1 H NMR (600 MHz, CDCl 3 ): δ = 7.20 (d, 3 J HH = 8.6 Hz, 2H), 6.72 (d, 3 J HH = 8.6 Hz, 2H), 5.94 (ddt, 3 J HH = 16.8, 3 J HH = 10.1, 3 J HH = 6.1 Hz, 1H), 5.19 (dq, 3 J HH = 16.8, 4 J HH = 2 J HH = 1.6 Hz, 1H), 5.10 (dq, 3 J HH = 10.1, 4 J HH = 2 J HH = 1.6 Hz, 1H), 3.70 (s, 2H), 3.27 (dt, 3 J HH = 6.1, 4 J HH = 1.6 Hz, 2H), 2.94 (s, 6H), 1.38 (br s, 1H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ): δ = 149.9, 136.9, 129.2, 128.2, 115.9, 112.7, 52.8, 51.7, 40.8. N-(4-Fluorobenzyl)prop-2-en-1-amine (2f):[30a] Colorless liquid (71 mg, 86 % isolated yield). 1 H NMR (600 MHz, CDCl 3 ): δ = 7.32-7.27 (m, 2H), 7.04-6.98 (m, 2H), 5.92 (ddt, 3 J HH = 17.1, 3 J HH = 10.2, 3 J HH = 5.9 Hz, 1H), 5.19 (dq, 3 J HH = 17.1, 4 J HH = 2 J HH = 1.4 Hz, 1H), 5.12 (dq, 3 J HH = 10.2, 4 J HH = 2...

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Section: Resultsmentioning

confidence: 91%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Nickel(II) Catalyzed Hydroboration: A Route to Selective Reduction of Aldehydes and N‐Allylimines

Hossain

Schmidt

2020

Eur J Inorg Chem

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“…To date, most reports on catalytic hydrosilylation have been focused on precious metals such as Ru, Rh, Ir or Pt; [2] however the scarcity and high cost of these metals press the need for cheaper and more abundant alternatives. Accordingly, over the past decade, we have witnessed the development of efficient catalysts based on first‐row transition metals, [5] being iron the metal that dominates the field, whereas studies with other metals such as nickel are less common [6–22] …”

Section: Introductionmentioning

confidence: 99%

Hydrosilylation of Carbonyl Compounds Catalyzed by a Nickel Complex Bearing a PBP Ligand

et al. 2021

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The efficient catalytic hydrosilylation of ketones and aldehydes has been investigated using a nickel pincer hydride complex supported by a diphosphino‐boryl ligand (PBP). It was found that the presence of the boryl group within the skeleton of the ligand has a beneficial effect on the catalytic activities observed for ketones compared to related pincer systems. The analysis of the reaction mechanism allows for the synthesis and characterization of a nickel alkoxide derivative by insertion of the carbonyl moiety into the Ni−H bond. Combined experimental and theoretical analysis (DFT) support a reaction mechanism that involves the initial formation of an alkoxide complex followed by reaction with the silane to release the corresponding silyl ether and regenerate the catalyst.

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“…It has been reported that the hydrosilylation of alkynes or alkenes can be effectively catalyzed using Wilkinson's catalyst (Rh(PPh 3 ) 3 Cl) . In this catalytic process, the organic phosphine ligands play a significant role in the hydrosilylation reaction . A series of rhodium catalysts with PEG‐based ionic liquids have been used as efficient and recyclable catalyst systems for hydrosilylation reactions…”

Section: Introductionmentioning

confidence: 99%

Synthesis of novel poly(ethylene glycol)‐containing imidazolium‐functionalized phosphine ligands and their application in the hydrosilylation of olefins

Zhang

Yang

et al. 2018

Applied Organom Chemis

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A series of polyethylene glycol-containing imidazolium-functionalized phosphine ligands (mPEG-im-PPh 2 ) were successfully synthesized and used in the rhodium-catalyzed hydrosilylation of olefins. The results indicate that the RhCl 3 /mPEG-im-PPh 2 catalytic system exhibits both excellent activity and selectivity for the β-adduct. In addition, the catalytic system may be recycled at least six times.

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Selective hydrosilylation of alkynes and ketones: contrasting reactivity between cationic 3-iminophosphine palladium and nickel complexes

Cited by 26 publications

References 51 publications

Nickel(II) Catalyzed Hydroboration: A Route to Selective Reduction of Aldehydes and N‐Allylimines

Nickel(II) Catalyzed Hydroboration: A Route to Selective Reduction of Aldehydes and N‐Allylimines

Hydrosilylation of Carbonyl Compounds Catalyzed by a Nickel Complex Bearing a PBP Ligand

Synthesis of novel poly(ethylene glycol)‐containing imidazolium‐functionalized phosphine ligands and their application in the hydrosilylation of olefins

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