AI Article Synopsis
- - The thermolysis of -BH in benzene at 200 °C produces various phenylated borane species, with the main product being a monophenylated compound, 5-Ph--BH, found in 48% yield.
- - Alongside the primary product, some minor products include 6-Ph--BH, which can convert to another form under UV light, and a new diphenylated compound, 5,8-Ph--BH.
- - These phenylated derivatives not only enhance the understanding of the assembly and structure of -BH but also exhibit strong blue fluorescence, marking the first instance of directly phenylating -BH, paving the way for producing luminescent organic-bor
Article Abstract
As a preliminary step toward its condensation into the porous polymer , the thermolysis of -BH () in benzene at 200 °C results in the generation of a number of phenylated borane molecular species. The principal product is the new monophenylated compound 5-Ph--BH (), isolated in 48% yield (based on consumption of ) and structurally characterized by single-crystal X-ray diffraction analysis, NMR, and mass spectrometry along with other minor products, such as 6-Ph--BH (), for which we observe UV-light-driven conversion into via a "vertex-flip" mechanism, and novel diphenylated 5,8-Ph--BH (). Together, the phenylated derivatives provide a valuable insight into the assembly of and ultimately inform on its structure. The new compounds also display strong blue fluorescence in both solid-state and in solution and are the first examples of the direct phenylation of -BH, thus opening the door to the straight-forward synthesis of highly luminescent organic-borane hybrid systems.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.joc.2c00997 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Electrostatically tuning radical addition and atom abstraction reactions with distonic radical ions.
Chem Sci
January 2025
Molecular Horizons and School of Chemistry and Molecular Bioscience, University of Wollongong Wollongong New South Wales 2522 Australia
Although electrostatic catalysis can enhance the kinetics and selectivity of reactions to produce greener synthetic processes, the highly directional nature of electrostatic interactions has limited widespread application. In this study, the influence of oriented electric fields (OEF) on radical addition and atom abstraction reactions are systematically explored with ion-trap mass spectrometry using structurally diverse distonic radical ions that maintain spatially separated charge and radical moieties. When installed on rigid molecular scaffolds, charged functional groups lock the magnitude and orientation of the internal electric field with respect to the radical site, creating an OEF which tunes the reactivity across the set of gas-phase carbon-centred radical reactions.
View Article and Find Full Text PDFCu-Catalyzed Diastereo- and Enantioselective Synthesis of Borylated Cyclopropanes with Three Contiguous Stereocenters.
J Am Chem Soc
January 2025
Frontiers Science Center for Transformative Molecules, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
Direct synthesis of enantioenriched scaffolds with multiple adjacent stereocenters remains an important yet challenging task. Herein, we describe a highly diastereo- and enantioselective Cu-catalyzed alkylboration of cyclopropenes, with less reactive alkyl iodides as electrophiles, for the efficient synthesis of -substituted borylated cyclopropanes bearing three consecutive stereocenters. This protocol features mild conditions, a broad substrate scope, and good functional group tolerance, affording an array of chiral borylated cyclopropanes in good to high yields with excellent diastereo- and enantioselectivities.
View Article and Find Full Text PDFEvaluation of Cereblon-Directing Warheads for the Development of Orally Bioavailable PROTACs.
J Med Chem
January 2025
Department of Chemical Biology and Therapeutics, St. Jude Children's Research Hospital, Memphis, Tennessee 38105, United States.
PROTACs usually occupy physicochemical space outside the one defined by classical drug-like molecules, which often presents considerable challenges in their optimization and development for oral administration. We have previously reported phenyl glutarimide (PG)-based BET PROTAC SJ995973, with improved overall degradation and antiproliferative activities compared to its direct thalidomide-based analogue dBET1, but similarly poor pharmacokinetic profile. To further demonstrate the PG utility, we describe here optimization efforts that led to the discovery of an orally bioavailable BET-PROTAC SJ44236 (), and results of a comprehensive comparative study with analogues containing alternative CRBN-directing warheads.
View Article and Find Full Text PDFAdding colour to ion-selective membranes.
Talanta
January 2025
Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093, Warsaw, Poland. Electronic address:
An idea of using ion-exchanger salt containing optically active cations to prepare ion-selective membranes is proposed. Although the presence of an ion-exchanger in the composition of neutral ionophore based sensors is necessary, the choice of available salts for cation-selective sensors preparation, is usually limited to sodium or potassium compounds. In this work we propose application of an alternative salt, using a cation optically active both in absorption and emission mode as a mobile one.
View Article and Find Full Text PDFEnhancing activity and selectivity of palladium catalysts in ketone α-arylation by tailoring the imine chelate of pyridinium amidate (PYA) ligands.
Catal Sci Technol
December 2024
Department of Chemistry, Biochemistry and Pharmaceutical Sciences, University of Bern Freiestrasse 3 3012 Bern Switzerland
Even though α-arylation of ketones is attractive for direct C-H functionalization of organic substrates, the method largely relies on phosphine-ligated palladium complexes. Only recently, efforts have focused on developing nitrogen-based ligands as a more sustainable alternative to phosphines, with pyridine-functionalized pyridinium amidate (pyr-PYA) ,'-bidentate ligands displaying good selectivity and activity. Here, we report on a second generation set of catalyst precursors that feature a 5-membered N-heterocycle instead of a pyridine as chelating unit of the PYA ligand to provide less steric congestion for the rate-limiting transmetalation of the enolate.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!