Selective derivatisation of resorcinarene ethers via an ortholithiation approach

Ngodwana, Lonwabo; Kleinhans, Dewald J.; Smuts, Anri-Jacques; Otterlo, Willem A. L. van; Arnott, Gareth E.

doi:10.1039/c3ra00141e

Cited by 13 publications

(22 citation statements)

References 31 publications

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“…Starting from the readily available octamethoxy resorcinarene 1 , we synthesized distal di(bromomethyl)resorcinarene 2b . Quenching the dilithiated intermediate with methyl iodide followed by radical bromination gave the desired dibromoresorcinarene 2 , but only in yields less than 20 % over the two steps.…”

Section: Resultsmentioning

confidence: 99%

“…Our prior work involved a protracted synthetic method for synthesis of the prerequisite distally functionalized resorcinarene. Fortunately, we were later able to improve on the method, allowing for rapid access to our distal‐substituted targets . Herein, we report our preliminary findings and successful synthesis and characterization of the first distally bridged, bidentate resorcinarene bis(carbene) palladium complex and show its use in representative Suzuki–Miyaura and Tsuji–Trost reactions.…”

Section: Introductionmentioning

confidence: 94%

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A Bidentate Resorcinarene‐Based Palladium Carbene Complex

et al. 2017

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 94%

A Bidentate Resorcinarene‐Based Palladium Carbene Complex

et al. 2017

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“…NMR spectra were recorded with a Bruker Avance 600 spectrometer [600.13 MHz ( 1 H)], Bruker Avance 400 spectrometer [400 ( 1 H)], or Bruker Avance 300 spectrometer [300 MHz ( 1 H)]; chemical shifts are reported relative to the residual solvent peak (CHCl 3 : δ =7.26 ppm, CDCl 3 ). Derivatives 1 a – d were synthesized according to literature procedures . XRD patterns were obtained in reflection mode with an automatic Bruker D8 diffractometer by using nickel‐filtered CuK α radiation.…”

Section: Methodsmentioning

confidence: 99%

Green, Mild, and Efficient Friedel–Crafts Benzylation of Scarcely Reactive Arenes and Heteroarenes under On‐Water Conditions

et al. 2019

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Metal‐free Friedel–Crafts benzylation (FCB) of scarcely reactive arenes and heteroarenes was performed under on‐water conditions by an environmentally sustainable procedure. The catalytic strategy exploits the hydrophobicity of the resorcinarene macrocycle 1 a. The proposed mechanism is based on the activation of benzyl chloride by H‐bonding interactions with catalyst 1 a. In fact, under on‐water conditions the hydrophobic amplification of the strength of the H‐bonding interactions between the OH groups of the resorcinarene catalyst and the chlorine atom of benzyl chloride leads to polarization of the C−Cl bond, which consequently promotes electrophilic attack of the π nucleophile. Thus, many arenes and heteroarenes were efficiently benzylated under mild on‐water conditions by using resorcinarene 1 a as catalyst. The FCB of benzene is industrially relevant for the synthesis of diphenylmethane, and hence the on‐water procedure was extended to the gram‐scale synthesis of diphenylmethane, starting from benzene and benzyl chloride in the presence of resorcinarene catalyst 1 a.

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“…In general, less rigid resorcinarenes seem to be more reactive towards lithiation agents. [24] As a consequence, we changed to sec-butyllithium as a more reactive reagent towards a direct ortho-metalation of the phenylic position of 10. This led, after refining the application modus, to quantitative lithiation at -78°C.…”

Section: Educt Ratiomentioning

confidence: 99%