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Alkanoylation of quinazoline by nucleophilic aromatic substitution: Combined experimental and computational study |
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| Authors: | Yumiko Suzuki Naoto Iwata Kohei Dobashi Ryo Takashima Sundaram Arulmozhiraja Erika Ishitsubo Naoya Matsuo Hiroaki Tokiwa |
| Institution: | 1. Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioicho, Chiyoda-ku, Tokyo 102-8554, Japan;2. Department of Chemistry, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8501, Japan;3. Research Center for Smart Molecules, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8501, Japan |
| Abstract: | A combined experimental and computational study on the key intermediates of NHC-catalyzed acylation reaction, Breslow intermediates (BIs), has been conducted in order to achieve a direct nucleophilic alkanoylation of N-heterocycles. Various BI precursors are alternatively prepared and used in the reaction with 4-chloroquinazoline. The present study reveals that the intermediates having benzimidazole moiety serve as acylating agents for the introduction of straight-chain alkanoyl groups. Natural bond orbital analysis indicates that the reactivity of intermediates partly correlates to the occupancy of the πC-C bonds of the hydroxyl enamine moieties. The putative rate-determining step of the acylation reaction has been theoretically investigated. Several new 4-alkanoylquinazolines are synthesized using the BI precursors. |
| Keywords: | Nitrogen heterocycles Breslow intermediate Alkanoylation Natural bond orbital Corresponding author Department of Materials and Life Sciences Faculty of Science and Technology Sophia University 7-1 Kioicho Chiyoda-ku Tokyo 102-8554 Japan |
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