An efficient dynamic asymmetric catalytic system within a zinc-templated network

Serra-Pont, Anna; Alfonso, Ignacio; Solà, Jordi; Jimeno, Ciril

doi:10.1039/c9cc03958a

Cited by 14 publications

(25 citation statements)

References 35 publications

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“…17). 90 We demonstrated that the complex network thus generated, with several potential catalysts, actually simplified under the reaction conditions making the bifunctional species to predominate in a kind of thermodynamic self-sorting. As expected, this species also provided the highest reaction acceleration and stereoselectivity, improving the performance of the previous pyridine-based system at lower catalyst loading.…”

Section: Complex Systems Leading To Efficient Catalysismentioning

confidence: 91%

“…Moreover, its reversible nature made impossible the synthesis and isolation of the catalytic complex, and the network generated with the three-components mixture was a convenient (and actually the only) manner of utilizing it. 90 Thus, our approach illustrated how a dynamic system can cooperatively work for the formation of an active catalyst, even in the presence of other species in equilibrium, which are intrinsically needed for the function of the system.…”

Section: Complex Systems Leading To Efficient Catalysismentioning

confidence: 99%

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Exploiting complexity to implement function in chemical systems

2020

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Section: Complex Systems Leading To Efficient Catalysismentioning

confidence: 91%

Section: Complex Systems Leading To Efficient Catalysismentioning

confidence: 99%

Exploiting complexity to implement function in chemical systems

2020

Self Cite

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“…(the syn diastereomer predominated), and the ee was moderate (Table , entry 7). Additionally, acetone was also used affording final aldol product with excellent yield but modest ee (Table , entry 8) …”

Section: Internal or External Lewis Acid Assisted (Thio)urea Catalmentioning

confidence: 99%

Hydrogen Bonding and Internal or External Lewis or Brønsted Acid Assisted (Thio)urea Catalysts

Gimeno

Herrera

2019

Eur J Org Chem

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The obtainment of more active organocatalysts has promoted the search for new modes of activation and new organocatalytic systems. Inspired on the mode of activation of enzymes, organocatalysis has recently focused on the challenge to create an enzyme‐like “active site” giving access to hydrogen‐bond donors (HBDs) with enhanced activity. Therefore, the assembly of catalytic species, connected through multiple weak inter‐ or intramolecular interactions, is a young and emerging topic of research which could become in the future a powerful tool for asymmetric catalysis. In the area of (thio)ureas, different alternatives such as internal hydrogen bonds or the use of an internal or an external Lewis or Brønsted acid assisted catalysts have been developed. The pivotal publications recently reported covering this family of organocatalysts are proof of this importance. This review treats to illustrate these important and scarce examples and to show a plausible mode of activation for each one.

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“…We have previously investigated reaction networks of so-called dynamic covalent catalysts. [22][23][24][25][26] By connecting catalytically active components with reversible imine bonds (Figure 1a), catalysts capable of modifying their own molecular architecture are accessible. When incorporated into dynamic systems undergoing constitutional exchange, these compounds display self-resolving behavior.…”

Section: Introductionmentioning

confidence: 99%

Activated Self‐Resolution and Error‐Correction in Catalytic Reaction Networks**

Schaufelberger

Ramström

2021

Chemistry A European J

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Understanding the emergence of function in complex reaction networks is a primary goal of systems chemistry and origin-of-life studies. Especially challenging is to create systems that simultaneously exhibit several emergent functions that can be independently tuned. In this work, a multifunctional complex reaction network of nucleophilic small molecule catalysts for the Morita-Baylis-Hillman (MBH) reaction is demonstrated. The dynamic system exhibited triggered self-resolution, preferentially amplifying a specific catalyst/product set out of a many potential alternatives. By utilizing selective reversibility of the products of the reaction set, systemic thermodynamically driven error-correction could also be introduced. To achieve this, a dynamic covalent MBH reaction based on adducts with internal H-transfer capabilities was developed. By careful tuning of the substituents, rate accelerations of retro-MBH reactions of up to four orders of magnitude could be obtained. This study thus demonstrates how efficient self-sorting of catalytic systems can be achieved through an interplay of several complex emergent functionalities.

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An efficient dynamic asymmetric catalytic system within a zinc-templated network

Abstract: Enhanced cooperativity leading to high catalytic activity and stereoselectivity in the direct aldol reaction has been achieved through a complex network of simple species interacting reversibly.

Cited by 14 publications

References 35 publications

Exploiting complexity to implement function in chemical systems

Exploiting complexity to implement function in chemical systems

Hydrogen Bonding and Internal or External Lewis or Brønsted Acid Assisted (Thio)urea Catalysts

Activated Self‐Resolution and Error‐Correction in Catalytic Reaction Networks**

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