The iridium-catalyzed borylation of pyrene, using 4,4'-dimethyl-2,2'-bipyridine as the ligand, in the presence of t-BuOK, gave a mixture of 2,4,7,9-tetrakis(Bpin)pyrene (c4) and its 2,4,7,10-isomer (m4) in a 2.2:1 ratio, and the selectivity of the Ir-catalyzed borylation of pyrene is kinetically determined and can be influenced to some extent by the nature of the ligand.
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http://dx.doi.org/10.1021/jo5024014 | DOI Listing |
Dalton Trans
April 2024
Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta T2N 1N4, Canada.
The borylation of aryl substituted pyridines is an effective way of preparing B-N doped conjugated organic frameworks. Trihaloborane Lewis acids are often employed for this protocol, and may require further functionalization to replace the remaining halides on boron. We report a new, fully characterized, electrophilic borylating agent, (CF)B(κ-NTf), that smoothly incorporates a -B(CF) unit into the model substrate 2-phenylpyridine.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
March 2023
Department of Chemistry, The University of Chicago, Chicago, IL-60637, USA.
Covalent organic frameworks (COFs) have received broad interest owing to their permanent porosity, high stability, and tunable functionalities. COFs with long-range π-conjugation and photosensitizing building blocks have been explored for sustainable photocatalysis. Herein, we report the first example of COF-based energy transfer Ni catalysis.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2021
Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China.
Replacement of the allylic C=C-C unit with a N-B-N unit at each of the three zigzag edges of [4]triangulene gives rise to B N -[4]triangulene, which is envisioned to represent a key structural unit of a new hypothetical boron carbon nitride (BC N). A tert-butylated B N -[4]triangulene has been successfully synthesized by three-fold nitrogen-directed borylation, and the X-ray crystallographic analysis indicates that its slightly bent triangular polycyclic framework can be viewed as a 1,3,5-triphenylbenzene connected by three 4π-electron N-B-N units. The HN-B-NH moiety provides a dual hydrogen-bond donor, which forms H-bonds with halide or carboxylate anions in solution, and form DD-AA hydrogen-bond arrays with 2,7-di(tert-butyl)-pyrene-4,5,9,10-tetraone in the co-crystal.
View Article and Find Full Text PDFJ Am Chem Soc
July 2021
Department of Chemistry, Graduate School of Science, and Integrated Research Consortium on Chemical Sciences (IRCCS), Nagoya University, Furo, Chikusa, Nagoya 464-8602, Japan.
Heteroatom doping is a powerful strategy to alter the electronic structure of polycyclic aromatic hydrocarbons (PAHs). Especially boron doping endows PAH scaffolds with electron-accepting character and Lewis acidic centers. Herein, we report that embedding a five-membered borole ring into a polycyclic skeleton imparts the π-system with antiaromatic character and thereby induces unique properties and behavior.
View Article and Find Full Text PDFOrg Lett
June 2021
Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasugakoen, Kasuga-shi, Fukuoka 816-8580, Japan.
Herein, direct unreactive C-N borylation of aromatic amines by a photocatalyst was achieved. The C-N borylation of aromatic amines with bis(pinacolato)diboron (Bpin) proceeded using a pyrene catalyst under light irradiation to afford desired borylated products and aminoborane as a byproduct. The yield of the borylated product improved under a CO atmosphere which probably reduced the inhibitory effect of aminoborane.
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