Molecular recognition-based catalysis in nucleophilic aromatic substitution: a mechanistic study

Basílio, Nuno; García‐Río, Luis; Peña‐Gallego, Ángeles; Pérez‐Lorenzo, Moisés

doi:10.1039/c2nj40128b

Cited by 7 publications

(6 citation statements)

References 21 publications

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“…To further expand on the general applicability of active template rotaxane synthesis with crown ethers, we explored other potential reaction modes. Prompted by a recent report 55 of crown ether catalysis of S N Ar reactions between aryl halides and primary amines, we investigated rotaxane formation by N-arylation. This proved effective using different electrophiles: combining amine 5 and 24crown-8 1 with aryl fluoride 23 in the presence of Et 3 N produced aniline rotaxane 24 in 85% yield ( Fig.…”

Section: Resultsmentioning

confidence: 99%

Weak functional group interactions revealed through metal-free active template rotaxane synthesis

et al. 2020

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Modest functional group interactions can play important roles in molecular recognition, catalysis and self-assembly. However, weakly associated binding motifs are often difficult to characterize. Here, we report on the metal-free active template synthesis of [2]rotaxanes in one step, up to 95% yield and >100:1 rotaxane:axle selectivity, from primary amines, crown ethers and a range of C=O, C=S, S(=O) 2 and P=O electrophiles. In addition to being a simple and effective route to a broad range of rotaxanes, the strategy enables 1:1 interactions of crown ethers with various functional groups to be characterized in solution and the solid state, several of which are too weakor are disfavored compared to other binding modesto be observed in typical host-guest complexes. The approach may be broadly applicable to the kinetic stabilization and characterization of other weak functional group interactions.

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Section: Resultsmentioning

confidence: 99%

Weak functional group interactions revealed through metal-free active template rotaxane synthesis

et al. 2020

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“…62 However, with Tet-1 as the catalyst, we discovered ( Figure S27A) that the reaction is not just second order in the amine concentration but also second order in the Tet-1 concentration. Given this information, we can 63,64 write the rate laws for the PSPM reactions with cat = Edge-model or Triglyme as…”

Section: Organocatalytic Polymer Functionalization With Tet-1mentioning

confidence: 99%

Size-Selective Catalytic Polymer Acylation with a Molecular Tetrahedron

Sharafi

McKay

Ivancic

et al. 2020

Chem

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We report an original catalytic molecular tetrahedron. By threading through the cavity of the tetrahedron, polymeric substrates are unfolded or broken apart. Our catalyst distinguishes between polymer chains of different lengths, functionalizing the shorter polymers selectively over the longer ones-as a proof of concept for selective catalysis to modify polymers. Our findings advance the fundamental understanding of the thermodynamic and kinetic phenomena controlling the interactions between molecular cages and synthetic polymers, offering valuable ability to create complex materials in the future.

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“…Catalyst optimization: The success of the communication mechanism shown in Scheme 1 relies on the ability to create catalytic rotaxanes with active catalytic triglyme side chains, which stabilize [6,14] the tetrahedral intermediates arising during aminolysis. Although the catalytic activity of simple glymes for aminolysis in organic solvents is well-known, [6] it was not clear how to geometrically constrain a glycol chain on the ring of a rotaxane, while at the same time obtaining effective intramolecular glycol catalysis.…”

Section: Resultsmentioning

confidence: 99%

Selective Monofunctionalization Enabled by Reaction‐History‐Dependent Communication in Catalytic Rotaxanes

et al. 2020

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Selective monofunctionalization of substrates with distant, yet equally reactive functional groups is difficult to achieve, as it requires the second functional group to selectively modulate its reactivity once the first functional group has reacted. We now show that mechanically interlocked catalytic rings can effectively regulate the reactivity of stoppering groups in rotaxanes over a distance of about 2 nm. Our mechanism of communication is enabled by a unique interlocked design, which effectively removes the catalytic rings from the substrates by fast dethreading as soon as the first reaction has taken place. Our method not only led to a rare example of selective monofunctionalization, but also to a “molecular if function”. Overall, the study presents a way to get distant functional groups to communicate with each other in a reaction‐history‐dependent manner by creating linkers that can ultimately perform logical operations at the molecular level.

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Molecular recognition-based catalysis in nucleophilic aromatic substitution: a mechanistic study

Cited by 7 publications

References 21 publications

Weak functional group interactions revealed through metal-free active template rotaxane synthesis

Weak functional group interactions revealed through metal-free active template rotaxane synthesis

Size-Selective Catalytic Polymer Acylation with a Molecular Tetrahedron

Selective Monofunctionalization Enabled by Reaction‐History‐Dependent Communication in Catalytic Rotaxanes

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