Distal Allylic/Benzylic C−H Functionalization of Silyl Ethers Using Donor/Acceptor Rhodium(II) Carbenes
| Autor: | Huw M. L. Davies, Yannick T. Boni, Janakiram Vaitla |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
Allylic rearrangement
Silylation 010405 organic chemistry Chemistry chemistry.chemical_element General Medicine General Chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry Article Catalysis 0104 chemical sciences Rhodium chemistry.chemical_compound Surface modification Stereoselectivity Donor acceptor Carbene |
| Zdroj: | Angew Chem Int Ed Engl |
| ISSN: | 1521-3773 1433-7851 |
| DOI: | 10.1002/anie.201916530 |
| Popis: | Regio- and stereoselective distal allylic/benzylic C–H functionalization of allyl and benzyl silyl ethers was achieved using rhodium(II) carbenes derived from N-sulfonyltriazoles and aryldiazoacetates as carbene precursors. The bulky rhodium carbenes led to highly site-selective functionalization of less activated allylic and benzylic C–H bonds even in the presence of electronically preferred C–H bonds located α to oxygen. The dirhodium catalyst Rh(2)(S–NTTL)(4) is the most effective chiral catalyst for triazole-derived carbene transformations, whereas Rh(2)(S–TPPTTL)(4) works best for carbenes derived from aryldiazoacetates. The reactions afford a variety of δ-functionalized allyl silyl ethers with high diastereo- and enantioselectivity. The utility of the present method was demonstrated by its application to the synthesis of a 3,4-disubstituted L-proline scaffold. |
| Databáze: | OpenAIRE |
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