Nickel-catalyzed reduction of ketones with water and triethylsilane

Castellanos-Blanco, Nahury; Flores-Álamo, Marcos; Garcı́a, Juventino J.

doi:10.1016/j.ica.2017.06.035

Cited by 11 publications

(9 citation statements)

References 45 publications

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“…An asymmetric transfer hydrogenation of 4-fluoroacetophenone gives a high conversion with ( S , S )-1,2-bis(2,5-diisopropylphospholan-1-yl)ethane (( S , S )- i Pr-en-Duphos) and ( S , S )- i Pr-Duphos, along with a moderate ee . ( S )-BINAP is unreactive and ( S , S )-1,1′-bis(2,5-diethylphospholano)ferrocene (( S , S )-Et-Ferrocelane) leads to a lower conversion and ee . The research was extended to catalytic transfer hydrogenation of benzonitriles, and a 3:3:2:1 ratio of Ni(cod) 2 : DCPE: DCPEO: DCPEO 2 (where DCPEO is dicyclohexyl(2-(dicyclohexylphosphino)ethyl)phosphine oxide and DCPEO 2 is ethane-1,2-diylbis(dicyclohexylphosphine oxide)) is the most effective catalyst system due to less favorable binding of the phosphine oxide to the nickel center …”

Section: Hydrogenationsupporting

confidence: 57%

“…The proposed mechanism includes the formation of (dippe) 2 Ni, followed by the replacement of one of the DIPPE ligands with the ketone. The researchers also tested DCPE (2:1) and found that, while DIPPE requires a slightly higher temperature, the results are mostly the same …”

Section: Hydrogenationmentioning

confidence: 73%

“…The researchers also tested DCPE (2:1) and found that, while DIPPE requires a slightly higher temperature, the results are mostly the same. 520 An asymmetric transfer hydrogenation of 4-fluoroacetophenone gives a high conversion with (S,S)-1,2-bis(2,5-diisopropylphospholan-1-yl)ethane ((S,S)-i Pr-en-Duphos) and (S,S)-i Pr-Duphos, along with a moderate ee. (S)-BINAP is unreactive and (S,S)-1,1′-bis(2,5-diethylphospholano)ferrocene ((S,S)-Et-Ferrocelane) leads to a lower conversion and ee.…”

Section: Hydrogenation 91 Hmentioning

confidence: 99%

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Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis

et al. 2020

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A critically important process in catalysis is the formation of an active catalyst from the combination of a metal precursor and a ligand, as the efficacy of this reaction governs the amount of active catalyst. This Review is a comprehensive overview of reactions catalyzed by nickel and an added bidentate phosphine, focusing on the steps transforming the combination of precatalyst and ligand into an active catalyst and the potential effects of this transformation on nickel catalysis. Reactions covered include common cross-coupling reactions, such as Suzuki, Heck, Kumada, and Negishi couplings, addition reactions, cycloadditions, C−H functionalizations, polymerizations, hydrogenations, and reductive couplings, among others. Overall, the most widely used nickel precatalyst with free bidentate phosphines is Ni(cod) 2 , which accounts for ∼50% of the reports surveyed, distantly followed by Ni(acac) 2 and Ni(OAc) 2 , which account for ∼10% each. By compiling the reports of these reactions, we have calculated statistics of the usage and efficacy of each ligand with Ni(cod) 2 and other nickel sources. The most common bidentate phosphines are simple, relatively inexpensive ligands, such as DPPE, DCPE, DPPP, and DPPB, along with others with more complex backbones, such as DPPF and Xantphos. The use of expensive chiral phosphines is more scattered, but the most common ligands include BINAP, Me-Duphos, Josiphos, and related analogs.

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Section: Hydrogenationsupporting

confidence: 57%

Section: Hydrogenationmentioning

confidence: 73%

Section: Hydrogenation 91 Hmentioning

confidence: 99%

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Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis

et al. 2020

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“…During this present study, our prime focus was to control the undesired side reactions, such as the hydrogenation of a carbonyl group as well as the base-mediated coupling of ketones (Table and Supporting Information (SI) Tables S1 and S2). At this point, we realized that a combination of a suitable nickel catalyst with a nitrogen ligand is crucial for such monoselective transformations …”

Section: Resultsmentioning

confidence: 99%

Nickel-Catalyzed Alkylation of Ketone Enolates: Synthesis of Monoselective Linear Ketones

2018

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Herein we have developed a Ni-catalyzed protocol for the synthesis of linear ketones. Aryl, alkyl, and heteroaryl ketones as well as alcohols yielded the monoselective ketones in up to 90% yield. The catalytic protocol was successfully applied in to a gram-scale synthesis. For a practical utility, applications of a steroid derivative, oleyl alcohol, and naproxen alcohol were employed. Preliminary catalytic investigations involving the isolation of a Ni intermediate and defined Ni–H species as well as a series of deuterium-labeling experiments were performed.

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“…Historically, the pioneering reports by Ojima (in the early 1970s), on the rhodium-catalyzed hydrosilylation of CvO and CvN bonds, are commonly recognized as a step forward for the use of hydrosilanes as reducing agents. 44,45 These early studies were conducted by several efficient procedures utilizing transition-metal catalysts [46][47][48][49][50][51][52][53][54][55] and main-group species. [56][57][58][59][60][61][62] In this context, our attention was drawn in particular to the procedures utilizing s-block element species.…”

Section: Hydrosilylation Of Unsaturated Carbon-heteroatom (O N) Moiementioning

confidence: 99%