Academic Journal
Direct allylic C–H alkylation of enol silyl ethers enabled by photoredox–Brønsted base hybrid catalysis
| العنوان: | Direct allylic C–H alkylation of enol silyl ethers enabled by photoredox–Brønsted base hybrid catalysis |
|---|---|
| المؤلفون: | Ohmatsu, Kohsuke, Nakashima, Tsubasa, Sato, Makoto, Ooi, Takashi |
| المصدر: | Nature Communications ; volume 10, issue 1 ; ISSN 2041-1723 |
| بيانات النشر: | Springer Science and Business Media LLC |
| سنة النشر: | 2019 |
| الوصف: | Strategies for altering the reaction pathway of reactive intermediates are of significant importance in diversifying organic synthesis. Enol silyl ethers, versatile enolate equivalents, are known to undergo one-electron oxidation to generate the radical cations that spontaneously form electrophilic α-carbonyl radicals via elimination of the silyl groups. Here, we demonstrate that close scrutiny of the property of the radical cations as strong C–H acids enables the identification of a catalyst system consisting of an iridium-based photosensitizer and 2,4,6-collidine for the generation of nucleophilic allylic radicals from enol silyl ethers through one-electron oxidation-deprotonation sequence under light irradiation without the desilylation of the radical cation intermediates. The resultant allylic radicals engage in the addition to electron-deficient olefins, establishing the selective allylic C-H alkylation of enol silyl ethers. This strategy is broadly applicable, and the alkylated enol silyl ethers can be transformed into highly functionalized carbonyl compounds by exploiting their common polar reactivity. |
| نوع الوثيقة: | article in journal/newspaper |
| اللغة: | English |
| DOI: | 10.1038/s41467-019-10641-y |
| الاتاحة: | http://dx.doi.org/10.1038/s41467-019-10641-y https://www.nature.com/articles/s41467-019-10641-y.pdf https://www.nature.com/articles/s41467-019-10641-y |
| Rights: | https://creativecommons.org/licenses/by/4.0 ; https://creativecommons.org/licenses/by/4.0 |
| رقم الانضمام: | edsbas.5802A90C |
| قاعدة البيانات: | BASE |
| DOI: | 10.1038/s41467-019-10641-y |
|---|