| Autor: |
Biosca, Maria, Szabó, Kálmán J., Himo, Fahmi |
| Zdroj: |
The Journal of Organic Chemistry; April 2024, Vol. 89 Issue: 7 p4538-4548, 11p |
| Abstrakt: |
Density functional theory calculations have been performed to investigate the mechanism for the BINOL-catalyzed asymmetric homologation of alkenylboronic acids with CF3-diazomethane. The reaction proceeds via a chiral BINOL ester of the alkenylboronic acid substrate. The calculations reveal a complex scenario for the formation of the chiral BINOL-alkenylboronate species, which is the key intermediate in the catalytic process. The aliphatic alcohol additive plays an important role in the reaction. This study provides a rationalization of the stereoinduction step of the reaction, and the enantioselectivity is mainly attributed to the steric repulsion between the CF3group of the diazomethane reagent and the γ-substituent of the BINOL catalyst. The complex potential energy surface obtained by the calculations is analyzed by means of microkinetic simulations. |
| Databáze: |
Supplemental Index |
| Externí odkaz: |
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