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Negligible Substituent Effect as Key to Synthetic Versatility: a Computational-Experimental Study of Vinyl Ethers Addition to Nitrile Oxidesстатья Исследовательская статья
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 20 апреля 2022 г.
- Авторы: Kutskaya Anastasia M., Serkov Semyon A., Voronin Vladimir V., Ledovskaya Maria S., Polynski Mikhail V.
- Журнал: ChemistrySelect
- Том: 7
- Номер: 10
- Год издания: 2022
- Первая страница: e202200174
- DOI: 10.1002/slct.202200174
- Аннотация: Abstract A tangible substituent effect may be perceived as a good feature in developing an organic reaction. This work demonstrates that, on the contrary, a zero-slope Hammet plot should be sought. The synthesis of isoxazoles by consecutive cycloaddition of nitrile oxides to vinyl ethers and alcohols elimination was studied computationally and experimentally. We performed a Hammett study in silico to demonstrate a negligible substituent effect (i. e., broad substrate scope) in the addition of benzyl vinyl ether to nitrile oxides. The modeling was performed at the ωB97X-V/def2-TZVP//PBE0-D4/def2-TZVP+SMD(benzene) level of theory within the RIJCOSX approximation. The experimental evaluation validated the computational model. A versatile methodology for synthesizing substituted isoxazolines and isoxazoles was proposed as the main result. We present this work as a successful example of how quantum chemical modeling can re-boost the classic Hammett approach to the optimization and design of organic synthetic methodologies. We anticipate further Hammett studies in silico, considering the current trend for data-driven chemical research.
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