دورية أكاديمية
Development and Mechanistic Study of an Iron-Catalyzed Intramolecular Nitroso Ene Reaction of Nitroarenes
| العنوان: | Development and Mechanistic Study of an Iron-Catalyzed Intramolecular Nitroso Ene Reaction of Nitroarenes |
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| المؤلفون: | Van Vu, Jair N. Powell, Russell L. Ford, Pooja J. Patel, Tom G. Driver |
| سنة النشر: | 2023 |
| مصطلحات موضوعية: | Biophysics, Biochemistry, Microbiology, Biotechnology, Developmental Biology, Inorganic Chemistry, Hematology, Infectious Diseases, Virology, Chemical Sciences not elsewhere classified, ordered transition state, diastereoselectively construct benzoxazines, 50 ± 0, 5 kcal mol, order rate dependence, mechanistic investigations indicated, inverse kinetic order, reaction proceeds via, reaction rate revealed, 1 cal mol, abundant iron catalyst, 3 , 3 mol, reaction revealed, temperature dependence, mechanistic study, kinetic analysis, − 39, withdrawing substituents, triggered using |
| الوصف: | An intramolecular iron-catalyzed nitroso ene reaction was developed to afford six- or seven-membered N -heterocycles from nitroarenes using an earth-abundant iron catalyst and phenylsilane as the terminal reductant. The reaction can be triggered using as little as 3 mol % iron(II) acetate and 3 mol % 4,7-dimethoxyphenanthroline as the ligand. The scope of the reaction is broad and tolerates a range of electron-releasing or electron-withdrawing substituents on the nitroarene, and the ortho -substituent can be modified to diastereoselectively construct benzoxazines, dihydrobenzothiazines, tetrahydroquinolines, tetrahydroquinoxalines, or tetrahydrobenzooxazepines. Mechanistic investigations indicated that the reaction proceeds via a nitrosoarene intermediate; kinetic analysis of the reaction revealed a first-order rate dependence in catalyst, nitroarene, and silane concentration, and an inverse kinetic order in acetate was observed. The difference in rates between PhSiH 3 and PhSiD 3 was found to be 1.50 ± 0.09, and investigation of the temperature dependence of the reaction rate revealed the activation parameters to be Δ H ‡ = 13.5 kcal mol –1 and Δ S ‡ = −39.1 cal mol –1 K –1 . These data were interpreted to indicate that the turnover-limiting step is hydride transfer from iron to the coordinated nitroarene, which occurs through an ordered transition state with little Fe–H bond breaking. |
| نوع الوثيقة: | article in journal/newspaper |
| اللغة: | unknown |
| العلاقة: | https://figshare.com/articles/journal_contribution/Development_and_Mechanistic_Study_of_an_Iron-Catalyzed_Intramolecular_Nitroso_Ene_Reaction_of_Nitroarenes/24528960Test |
| DOI: | 10.1021/acscatal.3c04483.s001 |
| الإتاحة: | https://doi.org/10.1021/acscatal.3c04483.s001Test https://figshare.com/articles/journal_contribution/Development_and_Mechanistic_Study_of_an_Iron-Catalyzed_Intramolecular_Nitroso_Ene_Reaction_of_Nitroarenes/24528960Test |
| حقوق: | CC BY-NC 4.0 |
| رقم الانضمام: | edsbas.CAB8F3C1 |
| قاعدة البيانات: | BASE |
| DOI: | 10.1021/acscatal.3c04483.s001 |
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