Electronic Resource
Mechanistic Insights into the DABCO-Catalyzed Cloke–Wilson Rearrangement: A DFT Perspective
| العنوان: | Mechanistic Insights into the DABCO-Catalyzed Cloke–Wilson Rearrangement: A DFT Perspective |
|---|---|
| المؤلفون: | Gallardo-Fuentes, Sebastián, Lodeiro, Lucas, Matute, Ricardo, Fernández López, Israel |
| بيانات النشر: | ACS Publications 2024-07-04T13:09:14Z 2024-07-04T13:09:14Z 2023-10-27 |
| نوع الوثيقة: | Electronic Resource |
| مستخلص: | The mechanism and selectivity patterns of the DABCO-catalyzed Cloke–Wilson rearrangement were computationally studied in detail using density functional theory calculations. Our computations suggest that the process occurs stepwise involving the initial ring opening of the cyclopropane promoted by a DABCO molecule followed by a ring-closure reaction of the readily formed zwitterionic intermediate. The regioselectivity of the initial nucleophilic ring-opening step strongly depends on the nature of the substituent attached to the cyclopropane moiety. The physical factors governing the preference for the more sterically hindered C2 (tertiary) position have been quantitatively analyzed by applying the combined activation strain model–energy decomposition analysis method. In addition, our calculations revealed a new mechanism for the analogous transformation involving vinylcyclopropanes consisting of an initial SN2′ ring-opening process followed by a 5-exo-trig cyclization step, which proceeds without facial selectivity. Depto. de Química Orgánica Fac. de Ciencias Químicas TRUE pub Descuento UCM |
| مصطلحات الفهرس: | 547, Ciencias, 2306 Química Orgánica, journal article, VoR |
| URL: | J. Org. Chem. 2023, 88, 22, 15902–15912 Publication Date:October 26, 2023 |
| الاتاحة: | Open access content. Open access content Attribution 4.0 International http://creativecommons.org/licenses/by/4.0 open access |
| ملاحظة: | application/pdf 1520-6904 English |
| Other Numbers: | ESRCM oai:docta.ucm.es:20.500.14352/105626 0022-3263 1520-6904 10.1021/acs.joc.3c02011 1449910654 |
| المصدر المساهم: | REPOSITORIO E-PRINTS UNIVERSIDAD COMPLU From OAIster®, provided by the OCLC Cooperative. |
| رقم الانضمام: | edsoai.on1449910654 |
| قاعدة البيانات: | OAIster |
| الوصف غير متاح. |