Catalytic Asymmetric Radical-Polar Crossover Hydroalkoxylation.
| Autor: | Discolo CA; Department of Chemistry , University of California , Irvine , California 92697-2025 , United States., Touney EE; Department of Chemistry , University of California , Irvine , California 92697-2025 , United States., Pronin SV; Department of Chemistry , University of California , Irvine , California 92697-2025 , United States. |
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| Jazyk: | angličtina |
| Zdroj: | Journal of the American Chemical Society [J Am Chem Soc] 2019 Nov 06; Vol. 141 (44), pp. 17527-17532. Date of Electronic Publication: 2019 Oct 25. |
| DOI: | 10.1021/jacs.9b10645 |
| Abstrakt: | Asymmetric intramolecular hydrofunctionalization of tertiary allylic alcohols is described. This metal hydride-mediated catalytic radical-polar crossover reaction delivers corresponding epoxides in good to high enantioselectivity and constitutes the first example of asymmetric hydrogen atom transfer-initiated process. A series of modified cobalt salen complexes has proven optimal for achieving good efficiency and asymmetric induction. Experimental data suggest that cationic cobalt complexes may be involved in the enantiodetermining step, where cation-π interactions in the catalyst contribute to the asymmetric induction. |
| Databáze: | MEDLINE |
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