We present a solvent-free thermo-mechanochemical approach for the direct coupling of carboxylic acids and amines, which avoids activators and additives. Detailed analysis of the reactions by and monitoring methods led to the observation, isolation, and characterisation of multicomponent crystalline intermediates that precede the formation of amides. We applied our methodology for the quantitative synthesis of the active pharmaceutical ingredient moclobemide.
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http://dx.doi.org/10.1039/d3cc04448c | DOI Listing |
Nat Commun
December 2024
Key Laboratory of Special Functional and Smart Polymer Materials of Ministry of Industry and Information Technology, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi'an, Shaanxi, China.
Coordination complexes are promising candidates for powerful electrocatalytic oxygen evolution reaction but challenges remain in favoring the kinetics behaviors through local coordination regulation. Herein, by refining the synergy of carboxylate anions and multiconjugated benzimidazole ligands, we tailor a series of well-defined and stable coordination complexes with three-dimensional supramolecular/coordinated structures. The coordinated water as potential open coordination sites can directly become intermediates, while the metal center easily achieves re-coordination with water molecules in the pores to resist lattice oxygen dissolution.
View Article and Find Full Text PDFJACS Au
December 2024
Key Laboratory of Molecular Enzymology and Engineering of Ministry of Education, School of Life Sciences, Jilin University, Changchun 130023, P. R. China.
In this study, we developed a machine-learning-aided protein design strategy for engineering hemoglobin (VHb) as carbene transferase. A Natural Language Processing (NLP) model was used for the first time to construct an algorithm (EESP, enzyme enantioselectivity score predictor) and predict the enantioselectivity of VHb. We identified critical amino acid residue sites by molecular docking and established a simplified mutation library by site-saturated mutagenesis.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.
We present a six-step cascade that converts 1,3-distyrylbenzenes (-stilbenes) into nonsymmetric pyrenes in 40-60% yields. This sequence merges photochemical steps, ,-alkene isomerization, a 6π photochemical electrocyclization (Mallory photocyclization); the new bay region cyclization, with two radical iodine-mediated aromatization steps; and an optional aryl migration. This work illustrates how the inherent challenges of engineering excited state reactivity can be addressed by logical design.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
Jihua Hengye Electronic Materials Co. Ltd., Foshan, Guangdong Province 528200, P. R. China.
Charge generation layers (CGLs) play crucial roles in determining the electroluminescence (EL) performance of tandem organic light-emitting diodes (OLEDs). However, acquiring negligible voltage drops across the CGL unit and high-efficiency multiplications remains challenging. Here, we propose barrier-free strategies to compose a high-performance p-i-n type CGL intermediate by introducing a Yb/HI-9 modification at the heterojunction and a novel n-dopant, Yb:1,3-bis(9-phenyl-1,10-phenanthrolin-2-yl)benzene (mdPPhen), as the n-CGL.
View Article and Find Full Text PDFChemistry
December 2024
Dipartimento di Scienze Molecolari e Nanosistemi, Universitá Ca' Foscari di Venezia, Via Torino 155, Mestre Venezia, Italy.
The supramolecular resorcinarene hexameric capsule efficiently promotes the unprecedented reaction between isocyanides and electron-deficient aromatic aldehydes leading to the formation of imines and carbon monoxide. The mechanism of the reaction was investigated via isotope labelling, kinetic analysis of the reaction, computational studies and the independent synthesis of a proposed intermediate. Control experiments indicate that the formation of the key aziridinone intermediate is limited to the cavity of the capsule.
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