Can hydrogen-bonding donors abstract chloride from LAu(I)Cl complexes: a computational study

Gung, Benjamin W.; Schlitzer, Steven C.

doi:10.1016/j.tetlet.2015.07.019

Cited by 5 publications

(3 citation statements)

References 46 publications

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“…These H‐bond donor groups were chosen for their well‐known ability to aid chloride abstraction from organic molecules [18] . Herein, we envisaged abstracting the chloride from an electrophilic metal center, with the intention of translating this common “anion‐binding” organocatalytic activation strategy to the realm of metal catalysis [19] . This concept sets the present work apart from the very few previous reports on Au(I) [20,21] or Pt(II) [22] complexes with tethered ureas or squaramides, where the pendant HBD groups fulfil the more conventional role of activating organic substrates via H‐bonding [23] …”

Section: Introductionmentioning

confidence: 99%

Silver‐Free Au(I) Catalysis Enabled by Bifunctional Urea‐ and Squaramide‐Phosphine Ligands via H‐Bonding

Franchino

Martí

Nejrotti

et al. 2021

Chemistry A European J

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A library of gold(I) chloride complexes with phosphine ligands incorporating pendant (thio)urea and squaramide H‐bond donors was prepared with the aim of promoting chloride abstraction from Au(I) via H‐bonding. In the absence of silver additives, complexes bearing squaramides and trifluoromethylated aromatic ureas displayed good catalytic activity in the cyclization of N‐propargyl benzamides, as well as in a 1,6‐enyne cycloisomerization, a tandem cyclization‐indole addition reaction and the hydrohydrazination of phenylacetylene. Kinetic studies and DFT calculations indicate that the energetic span of the reaction is accounted by both the chloride abstraction step, facilitated by the bidentate H‐bond donor via an associative mechanism, and the subsequent cyclization step.

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Section: Introductionmentioning

confidence: 99%

Silver‐Free Au(I) Catalysis Enabled by Bifunctional Urea‐ and Squaramide‐Phosphine Ligands via H‐Bonding

Franchino

Martí

Nejrotti

et al. 2021

Chemistry A European J

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“…Squaramide derivatives are well characterised as ditopic receptors, both experimentally and computationally. [45][46][47][48][49][50][51][52][53][54][55][56][57] Squaramide-based receptors, decorated with aromatic motifs, are able to establish strong hydrogen bonding interactions with halides, showing a greater binding affinity then the analogous urea based receptors. 55 Given their abilities as anion receptors, as well as their applicability in the field of medicinal chemistry, [58][59][60][61][62][63] squaramide derivatives have been studied as anion transporters.…”

Section: Introductionmentioning

confidence: 99%

Full elucidation of the transmembrane anion transport mechanism of squaramides using in silico investigations

Marques

Costa

Miranda

et al. 2018

Phys. Chem. Chem. Phys.

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A comprehensive experimental and theoretical investigation of the transmembrane chloride transport promoted by four series of squaramide derivatives, with different degrees of fluorination, number of convergent N-H binding units and conformational shapes, is reported. The experimental chloride binding and transport abilities of these small synthetic molecules in liposomes were rationalised with quantum descriptors and molecular dynamics simulations in POPC bilayers. The tripodal tren-based compounds, with three squaramide binding motifs, have high chloride affinity, isolating the anion from water molecules within the membrane model and preventing its release to the aqueous phase, in agreement with the absence of experimental transport activity. In contrast, the symmetrical mono-squaramides, with moderate chloride binding affinity, are able to bind and release chloride either in the aqueous phase or at the membrane interface level, in line with experimentally observed high transport activity. The PMF profiles associated with the diffusion of these free transporters and their chloride complexes across phospholipid bilayers show that the assisted chloride translocation is thermodynamically favoured.

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“…Great efforts have been made to design ancillary ligands which possess functional groups that can interact with substrates and solvent molecules in such a way that the Au–Cl bond is rendered more labile, and catalysis becomes possible. 8 Hydrogen bonding plays a pivotal role in such systems 9 and recent examples include phosphines bearing fluorinated amide groups, 10 a a phosphine bearing a phosphoric acid function, 10 b NHCs with secondary amine moieties, 10 c phosphanoxy-substituted phosphaalkenes, 10 d and squaramide- or urea-functionalized phosphines. 10 e Another recent advance is the use of additives that operate via halogen bonding and are capable of activating the Au–Cl bond leading to catalytically active species.…”

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confidence: 99%

Hydrogen bonding-enabled gold catalysis: ligand effects in gold-catalyzed cycloisomerizations in hexafluoroisopropanol (HFIP)

et al. 2022

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Can hydrogen-bonding donors abstract chloride from LAu(I)Cl complexes: a computational study

Cited by 5 publications

References 46 publications

Silver‐Free Au(I) Catalysis Enabled by Bifunctional Urea‐ and Squaramide‐Phosphine Ligands via H‐Bonding

Silver‐Free Au(I) Catalysis Enabled by Bifunctional Urea‐ and Squaramide‐Phosphine Ligands via H‐Bonding

Full elucidation of the transmembrane anion transport mechanism of squaramides using in silico investigations

Hydrogen bonding-enabled gold catalysis: ligand effects in gold-catalyzed cycloisomerizations in hexafluoroisopropanol (HFIP)

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