The synthesis of sterically hindered α-arylated acetamides generally requires a multistep reaction sequence and is also difficult to access due to steric constraints. This protocol allows the synthesis of sterically hindered α-arylated acetamides in moderate to high yields via 1,6-addition of isocyanides to p-quinone methides in the presence of BF .OEt . The present transformation features transition metal-free conditions, avoiding the use of toxic carbon monoxide, broad substrate scope, mild reaction conditions, and operational simplicity.
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http://dx.doi.org/10.1002/asia.202200642 | DOI Listing |
The synthesis of a transient cationic phosphaborene [(Mes*)P=B(CAAC)]+ (Mes* = 2,4,6,-trit-tert-butylphenyl, CAAC = cyclic alkylamino carbene) by halide abstraction from the B-brominated analogue is reported. This species was found to undergo rapid and selective intramolecular aliphatic C-H bond activation to yield a phosphinoborenium cation, which undergoes facile deprotonation to give a cyclic base-stabilized phosphaborene. Computational investigation of the mechanism of C-H activation indicates a boron-centred activation route with an exceptionally low barrier of 8 kJ mol-1, followed by a nearly barrierless hydride migration from boron to phosphorus.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Institute for Molecular Science, Myodaiji, Okazaki, 444-8787, Japan.
The synthesis and characterization of fused aromatic networks composed of zinc tetrapyrazinoporphyrazines are reported. The steric repulsion of bulky substituents induced the formation of three-dimensional structures. Thus-obtained insoluble polymers adsorbed CO and had near-infrared absorption indicating their porosity and extended π-conjugation.
View Article and Find Full Text PDFACS Nano
January 2025
Conte Center for Polymer Research, Polymer Science and Engineering, University of Massachusetts Amherst, Amherst, Massachusetts 01003, United States.
Bottlebrush block copolymers (BBCPs) are a unique class of materials that contain a backbone with densely grafted and chemically distinct polymeric side chains. The nonlinear architecture of BBCPs provides numerous degrees of freedom in their preparation, including control over key parameters such as grafting density, side chain length, block arrangement, and overall molecular weight. This uniquely branched structure provides BBCPs with several important distinctions from their linear counterparts, including sterically induced side chain and backbone conformations, rapid and large self-assembled nanostructures, and reduced or eliminated entanglement effects (assuming sufficient grafting density and that the molecular weight of the side chains is below their respective entanglement molecular weight).
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China.
The comprehensive understanding of the effect of the chemical environment surrounding active sites on the pathway for the electrochemical carbon dioxide reduction reaction (eCORR) is essential for the development of advanced catalysts for large-scale applications. Based on a series of model catalysts engineered by the coordination of copper ions with various isomers of phenylenediamine [i.e.
View Article and Find Full Text PDFACS Omega
January 2025
Unit of Excellence in Computational Molecular Science and Catalysis, and Division of Chemistry, School of Science, University of Phayao, Phayao 56000, Thailand.
The effectiveness of metallocene catalysts in the cationic ring-opening polymerization (cationic ROP) of ε-caprolactone (CL) is influenced by the choice of metallocene/borate systems, particularly their bulkiness. Recent research examines this effect on the initiation and propagation stages of cationic ROP. We conducted a density functional theory study on the precatalyst activation of cationic CL ROP by zirconocene/borate catalysts, where four models of zirconocene precatalysts (CpZrMe (), (MeCp)CpZrMe (), (MeCp)ZrMe (), and IndZrMe ()) were combined with boron cocatalysts B(CF) and [X][B(CF) ] (X = PhC or PhMeNH).
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