We propose one-pot synthesis of siloles from readily available starting materials. This methodology is practical for the preparation of multisubstituted siloles in good to excellent yields with complete regioselectivity. Sequential reactions, such as lithiation, silylation, and diisobutylaluminum-hydride-promoted cyclization, enable the preparation of the siloles. This transformation provides siloles through two efficient C-Si bond formations in one vessel.
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http://dx.doi.org/10.1021/acs.joc.2c00847 | DOI Listing |
Phys Chem Chem Phys
October 2024
Department of Chemistry, Memorial University of Newfoundland, Core Science Facility, 45 Arctic Avenue, St. John's, NL A1C 5S7, Canada.
This paper describes a mechanistic study on double boron-silicon exchange reactions between dibenzosiloles and boron tribromide. This type of reaction presents a safe and environmentally benign approach to convert electron-rich siloles into corresponding electron-deficient boroles and hence shows intriguing potential for the synthesis of boron-doped π-conjugated molecular materials. However, the detailed mechanisms for such reactions have not yet been established in the current literature.
View Article and Find Full Text PDFMolecules
September 2024
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588, Japan.
Silole- and phosphole-containing polycyclic aromatic compounds have attracted significant attention in the field of organic functional materials. The structure of the aromatic units has great impact on the photophysical properties of the resulting silole- and phosphole-containing polycyclic aromatic compounds. Here, dibenzo-fused naphtho[2,3-:6,7-']disilole (NDS) and naphtho[2,3-:6,7-']diphosphole (NDP), where a naphthalene unit is arranged between two silole and phosphole units, respectively, were designed and synthesized.
View Article and Find Full Text PDFACS Appl Bio Mater
October 2024
Graduate School of Science and Engineering Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama, Saitama 338-8570, Japan.
Biomacromolecules are viewed as promising drugs due to their specific functions in biological processes, biocompatibility, and pharmacological efficacy. Injective administration, chosen to avoid intestinal barriers, may in turn lead to immediate decay in the circulation system, unreliable targeting performance, or the induction of immune responses. For some biomacromolecules, chemically modified proteins have been developed for practical use.
View Article and Find Full Text PDFChemistry
December 2024
Institute of Inorganic Chemistry, Academy of Sciences of the Czech Republic, Husinec-Řež 1001, 25068, Řež, Czech Republic.
We experimentally demonstrate a new type of the intramolecular reaction between non-activated alkyne units and the dialkylboryl group (9-BBN), which was previously only hypothesized and studied on a calculational level. The reaction described here can formally be classified as a 1,2-hydroboration reaction, but, in contrast to the classical mechanism via a cyclic four-membered transition state, the reaction proceeds by a pericyclic mechanism involving a six-membered transition state. In practice, the reaction allows the synthesis of a new class of the borolenes fused with silole or dihydrosilole units.
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June 2024
Graduate School of Advanced Science and Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan.
Germoles and siloles unsymmetrically condensed with heteroaromatic units are attracting much interest. In this study, compounds containing a triazologermole core unit condensed with a benzene or thiophene ring were prepared. Thienotriazologermole was subjected to bromination to obtain the bromide, which underwent transformation via the palladium-catalyzed Stille coupling reaction to form triphenylamine-substituted thienotriazolegermole, with an effective extension of conjugation.
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