| Autor: |
Davies TQ; Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany., Kim JY; Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany., Fürstner A; Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany. |
| Jazyk: |
angličtina |
| Zdroj: |
Journal of the American Chemical Society [J Am Chem Soc] 2022 Oct 19; Vol. 144 (41), pp. 18817-18822. Date of Electronic Publication: 2022 Oct 04. |
| DOI: |
10.1021/jacs.2c09328 |
| Abstrakt: |
The nickel catalyzed reductive coupling of aldehydes with sorbate esters and related electron-deficient 1,3-dienes are known in the literature to occur at the π-bond proximal to the ester to afford aldol-type products. In stark contrast to this established path, a VAPOL-derived phosphoramidite ligand in combination with a bench-stable nickel precatalyst brokers a regiocomplementary course in that C-C bond formation proceeds exclusively at the distal alkene site to give deoxypropionate type products carrying an acrylate handle; they can be made in either anti - or syn -configured form. In addition to this enabling reverse pathway, the reaction is distinguished by excellent levels of chemo-, diastereo-, and enantioselectivity; moreover, it can be extended to the catalytic formation of F 3 C-substituted stereogenic centers. The use of a dienyl pinacolboronate instead of a sorbate ester is also possible, which opens access to valuable chiral borylated building blocks in optically active form. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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