Substrate‐Induced Self‐Assembly of Cooperative Catalysts

Muñana, Pablo Solís; Ragazzon, Giulio; Dupont, Julien; Ren, Chloe Z.‐J.; Prins, Leonard J.; Chen, Jack L.‐Y.

doi:10.1002/anie.201810891

Cited by 93 publications

(48 citation statements)

References 56 publications

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“…Prins and Chen et al. demonstrated that a phosphate ester substrate can induce the formation of vesicular assemblies, which act as cooperative catalysts for hydrolysis of the same substrate . A substrate‐induced covalent assembly formation of chiral boroxinate catalysts has also been shown by Wulff et al.…”

Section: Methodssupporting

confidence: 71%

Substrate‐Induced Dimerization Assembly of Chiral Macrocycle Catalysts toward Cooperative Asymmetric Catalysis

et al. 2020

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An artificial system of substrate‐induced dimerization assembly of chiral macrocycle catalysts enables a highly cooperative hydrogen‐bonding activation network for efficient enantioselective transformation. These macrocycles contain two thiourea and two chiral diamine moieties and dimerize with sulfate to form a sandwich‐like assembly. The macrocycles then adopt an extended conformation and reciprocally complement the hydrogen‐bonding interaction sites. Inspired by the guest‐induced dynamic assembly, these macrocycles catalyze the decarboxylative Mannich reaction of cyclic aldimines containing a sulfamate heading group. The imine substrate can be activated toward nucleophilic attack of β‐ketoacid by a cooperative hydrogen‐bonding network enabled by sulfamate‐induced dimerization assembly of the macrocycle catalysts. Highly efficient (>95 % yield in most cases) and enantioselective (up to 97.5:2.5 er) transformation of a variety of substrates using only 5 mol % macrocycle was achieved.

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Section: Methodssupporting

confidence: 71%

Substrate‐Induced Dimerization Assembly of Chiral Macrocycle Catalysts toward Cooperative Asymmetric Catalysis

et al. 2020

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“…[28,29] Substrate-induced access of active conformation is also widely exploited in extant biology for accelerating catalysis. [33][34][35][36] In the present work, we show the out-of-equilibrium generation of ac onformationally distinct assembled state induced by substrate,accelerated catalysis,and relapse to the initial state ( Figure 1b). Simple amino acid based amphiphiles have been shown to access out-of-equilibrium helical morphology in presence of ak inetically stable ester.W es how evidence of the time-dependent generation of an ew phase, rate acceleration negative feedback and disassembly.…”

supporting

confidence: 59%

Designed Negative Feedback from Transiently Formed Catalytic Nanostructures

et al. 2019

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Highly dynamic and complex systems of microtubules undergo a substrate‐induced change of conformation that leads to polymerization. Owing to the augmented catalytic potential at the polymerized state, rapid hydrolysis of the substrate is observed, leading to catastrophe, thus realizing the out‐of‐equilibrium state. A simple synthetic mimic of these dynamic natural systems is presented, where similar substrate induced conformational change is observed and a transient helical morphology is accessed. Further, augmented catalytic potential of these helical nanostructures leads to rapid hydrolysis of the substrate providing negative feedback on the stability of the nanostructures and realization of an out‐of‐equilibrium state. This simple system, made from amino acid functionalized lipids, demonstrates a substrate‐induced self‐assembled state, where the fuel‐to‐waste conversion leads to the temporal presence of helical nanostructures.

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“…Inspired by biological system, research interests in supramolecular chemistry are now shifting to the implementation of out-of-equilibrium selfassembly in artificial scenario. [5] An important focus of out-ofequilibrium self-assembly is the selection of specific selfassembly pathways along ac orrugated self-assembly energy landscape,that leads to products temporarily or permanently retained in alocal rather than the global minimum. In recent efforts,s pecific pathways are selected through the employment of,e .g., rationally designed molecules, [6] or catalysts, [7] and features the formation of different out-of-equilibrium structures bearing different material properties while still employing the same building blocks.Despite these prospects, the current approaches towards kinetically controlled selfassembly remain scarce.…”

mentioning

confidence: 99%

Access to Metastable Gel States Using Seeded Self‐Assembly of Low‐Molecular‐Weight Gelators

et al. 2019

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Here we report on howm etastable supramolecular gels can be formed through seeded self-assembly of multicomponent gelators.Hydrazone-based gelators decorated with non-ionic and anionic groups are formed in situ from hydrazide and aldehyde building blocks,a nd lead through multiple self-sorting processes to the formation of heterogeneous gels approaching thermodynamic equilibrium. Interestingly,the addition of seeds composing of oligomers of gelators bypasses the self-sorting processes and accelerates the selfassembly along ak inetically favored pathway,r esulting in homogeneous gels of whichthe network morphologies and gel stiffness are markedly different from the thermodynamically more stable gel products.I mportantly,o ver time,t hese metastable homogeneous gel networks are capable of converting into the thermodynamically more stable state.This seedingdriven formation of out-of-equilibrium supramolecular structures is expected to serve as as imple approach towards functional materials with pathway-dependent properties.

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Substrate‐Induced Self‐Assembly of Cooperative Catalysts

Cited by 93 publications

References 56 publications

Substrate‐Induced Dimerization Assembly of Chiral Macrocycle Catalysts toward Cooperative Asymmetric Catalysis

Substrate‐Induced Dimerization Assembly of Chiral Macrocycle Catalysts toward Cooperative Asymmetric Catalysis

Designed Negative Feedback from Transiently Formed Catalytic Nanostructures

Access to Metastable Gel States Using Seeded Self‐Assembly of Low‐Molecular‐Weight Gelators

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