Mechanistic Studies on Rhodium-Catalyzed Enantioselective Silylation of Aryl C–H Bonds
| العنوان: | Mechanistic Studies on Rhodium-Catalyzed Enantioselective Silylation of Aryl C–H Bonds |
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| المؤلفون: | Taegyo Lee, John F. Hartwig |
| المصدر: | Journal of the American Chemical Society. 139:4879-4886 |
| بيانات النشر: | American Chemical Society (ACS), 2017. |
| سنة النشر: | 2017 |
| مصطلحات موضوعية: | Steric effects, Silylation, Stereochemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Biochemistry, Article, Catalysis, Rhodium, chemistry.chemical_compound, Colloid and Surface Chemistry, Molecule, Organosilicon Compounds, Bond cleavage, Molecular Structure, 010405 organic chemistry, Aryl, Enantioselective synthesis, Stereoisomerism, General Chemistry, 2-Norbornyl cation, 0104 chemical sciences, Kinetics, chemistry, Quantum Theory |
| الوصف: | Several classes of enantioselective silylations of C-H bonds have been reported recently, but little mechanistic data on these processes are available. We report mechanistic studies on the rhodium-catalyzed, enantioselective silylation of aryl C-H bonds. A rhodium silyl dihydride and a rhodium norbornyl complex were prepared and determined to be interconverting catalyst resting states. Kinetic isotope effects indicated that the C-H bond cleavage step is not rate-determining, but the C-H bond cleavage and C-Si bond-forming steps together influence the enantioselectivity. DFT calculations indicate that the enantioselectivity originates from unfavorable steric interactions between the substrate and the ligand in the transition state leading to the formation of the minor enantiomer. |
| تدمد: | 1520-5126 0002-7863 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::42e3bbea84577ce1aeca56e69d819643 https://doi.org/10.1021/jacs.7b00737 |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.doi.dedup.....42e3bbea84577ce1aeca56e69d819643 |
| قاعدة البيانات: | OpenAIRE |
Find this issue from the American Chemical Society | تدمد: | 15205126 00027863 |
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