Correlating electronic and catalytic properties of frustrated Lewis pairs for imine hydrogenation

Dorkó, Éva; Kótai, Bianka; Földes, Tamás; Gyömöre, Ádám; Pápai, Imre; Soós, Tibor

doi:10.1016/j.jorganchem.2017.04.031

Cited by 21 publications

(18 citation statements)

References 19 publications

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“…74 The reduction of (Z)-N-tert-butyl-1-phenylmethanimine using FLPs consisting of DABCO and a range of heteroleptic triarylboranes was demonstrated to glean trends behind catalytic hydrogenation activity (Scheme 25). 115 Conversions were generally found to increase with the total number of fluorines on the aryl rings, whilst the number of chlorine atoms had a negligible effect on catalytic activity. 115 The heteroleptic borane B(2-F-6-ClC6H3)(2,6-Cl2C6H3)2 was employed in FLP catalysed reductive aminations (30 examples, 26-95% yield) (Scheme 26).…”

Section: Flp Catalysed Hydrogenation Reactionsmentioning

confidence: 96%

“…115 Conversions were generally found to increase with the total number of fluorines on the aryl rings, whilst the number of chlorine atoms had a negligible effect on catalytic activity. 115 The heteroleptic borane B(2-F-6-ClC6H3)(2,6-Cl2C6H3)2 was employed in FLP catalysed reductive aminations (30 examples, 26-95% yield) (Scheme 26). This borane was chosen as a catalyst due to large steric hinderance of chlorine atoms in the ortho positions of the aryl rings inducing water tolerance.…”

Section: Flp Catalysed Hydrogenation Reactionsmentioning

confidence: 96%

“…114 Subsequent investigations concerned the preparation of heteroleptic boranes with the additional variation of methyl substituents on one of the three aryl rings (Scheme 10). 115 Variation at the meta and para positions of the nonmethylated aryl ring allowed for probes into the impact of the electronic effect on Lewis acidity, whilst variation of the Scheme 9: Synthesis of heteroleptic boranes bearing fluorinated and chlorinated aryl wingtip groups. 114 meta position on the methylated aryl ring allowed for investigation into steric effects.…”

Section: Synthesis Of Heteroleptic Halogenated Triarylboranesmentioning

confidence: 99%

“…115 By determining experimentally Lewis acidity via the Gutmann-Beckett method, it was found that replacing fluorine for hydrogen in the meta position enhanced the Lewis acidity of the borane, but introducing chlorine had negligible effects. 115 A range of asymmetrically substituted boranes were prepared to evaluate the change in acidity when fluorine atoms were gradually replaced with chlorine atoms in B(2-F-6-ClC6H3)3 (Scheme 11). 74 It was found that by increasing the number of chlorine atoms, the water tolerance of the borane increased.…”

Section: Synthesis Of Heteroleptic Halogenated Triarylboranesmentioning

confidence: 99%

“…157 Scheme 25: Imine reduction by a range of heteroleptic triaryl boranes. 115 Scheme 26: Water tolerant reductive amination by B(2-F-6-ClC6H3)(2,6-Cl2C6H3)2. 74 The reduction of (Z)-N-tert-butyl-1-phenylmethanimine using FLPs consisting of DABCO and a range of heteroleptic triarylboranes was demonstrated to glean trends behind catalytic hydrogenation activity (Scheme 25).…”

Section: Flp Catalysed Hydrogenation Reactionsmentioning

confidence: 99%

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Halogenated triarylboranes: synthesis, properties and applications in catalysis

2020

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Section: Flp Catalysed Hydrogenation Reactionsmentioning

confidence: 96%

Section: Flp Catalysed Hydrogenation Reactionsmentioning

confidence: 96%

Section: Synthesis Of Heteroleptic Halogenated Triarylboranesmentioning

confidence: 99%

Section: Synthesis Of Heteroleptic Halogenated Triarylboranesmentioning

confidence: 99%

Section: Flp Catalysed Hydrogenation Reactionsmentioning

confidence: 99%

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Halogenated triarylboranes: synthesis, properties and applications in catalysis

2020

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Synthetic Approaches to Triarylboranes from 1885 to 2020

Berger

Ferger

Marder

2021

Chemistry A European J

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In recent years, research in the fields of optoelectronics, anion sensors and bioimaginga gents have been greatly influenced by novel compounds containing triarylborane motifs. Such compounds possess an empty p-orbital at boron which resultsi nu seful optical and electronic properties. Such ad iversity of applications was not expected when the first triarylboranew as reported in 1885. Synthetic approaches to triarylboranes underwent variousc hanges over the following century,s ome of which are still used in the present day,s uch as the generally applicable routes developedb yK rause et al. in 1922developedb yK rause et al. in , or by Grisdale et al. in 1972 at Eastman Kodak. Some other developments were not pursued further after their initial reports, such as the synthesis of two triarylboranes bearing three different aromatic groups by Mikhailov et al. in 1958. This reviews ummarizes the developmento fs ynthetic approaches to triarylboranes from their first report nearly 135 years ago to the present.2021 The Authors. Chemistry -A European Journal published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properlyc ited.Selected by the EditorialO ffice for our Showcaseo fo utstanding Reviewtype articles (www.chemeurj.org/showcase).

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Rational Development of a Metal‐Free Bifunctional System for the C−H Activation of Methane: A Density Functional Theory Investigation

et al. 2021

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The activation or heterolytic splitting of methane, a challenging substrate usually restricted to transition metals, has so far proven elusive in experimental frustrated Lewis pair (FLP) chemistry. In this article, we demonstrate, using density functional theory (DFT), that 1-aza-9-boratriptycene is a conceptually simple intramolecular FLP for the activation of methane. Systematic comparison with other FLP systems allows to gain insight into their reactivity with methane. The thermodynamics and kinetics of methane activation are interpreted by referring to the analysis of the natural charges and by employing the distortion-interaction/activation strain (DIAS) model. These showed that the nature of the Lewis base influences the selectivity over the reaction pathway, with N Lewis bases favoring the deprotonation mechanism and P bases the hydride abstraction one. The lower barrier of activation for 1-aza-9boratriptycene and the higher products stability are due to a better interaction energy than its counterparts, itself due to electrostatic interactions with the methane moiety, favorable orbital overlaps allowed by the side-attack, and space proximity between the B and N atoms.

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Correlating electronic and catalytic properties of frustrated Lewis pairs for imine hydrogenation

Cited by 21 publications

References 19 publications

Halogenated triarylboranes: synthesis, properties and applications in catalysis

Halogenated triarylboranes: synthesis, properties and applications in catalysis

Synthetic Approaches to Triarylboranes from 1885 to 2020

Rational Development of a Metal‐Free Bifunctional System for the C−H Activation of Methane: A Density Functional Theory Investigation

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