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

Abstract

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.

Polymerization, Stimuli‐induced Depolymerization, and Precipitation‐driven Macrocyclization in a Nitroaldol Reaction System**

“…Dual entrypoint equilibration analysis. Performed using model system in deuterated acetonitrile in the presence of Et 3 N [64] . From starting components: 2‐pyridinecarboxaldehyde ( 4 ) and 1‐nitropropane ( 5 ) were mixed in anhydrous CD 3 CN and stirred at rt under N 2 .…”

“…Dual entrypoint equilibration analysis. Performed using model system in deuterated acetonitrile in the presence of Et 3 N. [64] From starting components: 2‐pyridinecarboxaldehyde ( 4 ) and 1‐nitropropane ( 5 ) were mixed in anhydrous CD 3 CN and stirred at rt under N 2 . Et 3 N (10 mol %) was added and the reaction was followed by NMR over time, indicating that equilibrium was reached within 24 h. From product: 2‐nitro‐1‐(pyridin‐2‐yl)butan‐1‐ol ( 6 ) was dissolved in anhydrous CD 3 CN and stirred at r.t. under N 2 .…”

Self-healable, Regenerable, and Degradable Dynamic Covalent Nitroalcohol Organogels

“…To evaluate the proposed crosslinking reaction, a dual entry-point equilibration study was initially performed on a model system (Figure 1b, Figure S1). 1,66 The reaction of trialdehyde 1 with monotopic 1-nitropropane (4) in deuterated dimethylsulfoxide (DMSO-d₆) was triggered by adding triethylamine as the catalyst. As shown in the ¹H-NMR spectrum (Figure 1d), upon reaching equilibrium, nitroaldol adducts (○) were produced in the presence of small amounts of partially-reacted trialdehyde (◐), and the starting nitroalkane (▽).…”

Cheap Turns Superior: A Linear Regression-Based Correction Method to Reaction Energy from the DFT

“…The use of lower-level methods can incur significant errors that are difficult to anticipate. Thus, a computational model of reaction networks to predict chemical outcomes using low-level DFT-derived energies may lead to erroneous conclusions. − This type of error in reaction energies can be reduced impromptu, as shown by Christensen et al In contrast, the choice of higher-level methods (e.g., hybrid or meta-hybrid DFT) would require high computational cost and is infeasible to use for large networks . Furthermore, accuracy is not always guaranteed, even for higher-level DFT methods .…”