11° SEMINARIO QUÍMICA ORGÁNICA IQUIR 2020

SEMINARIO QUÍMICA ORGÁNICA 27-07-20
TÍTULO: "Enantioselective Diarylcarbene Insertion into Si-H Bonds Induced by Electronic Properties of the Carbenes"
FUENTE: Liang-liang Yang, Declan Evans, Bin Xu, Wen-Tao Li, Mao-Lin Li, Shou-Fei Zhu, K. N. Houk, and Qi-Lin Zhou J. Am. Chem. Soc. 2020, 142, 12394-12399, DOI:10.1021/jacs.0c04725.
EXPOSITOR: Lic. Iván Cortés
DÍA, HORA y LUGAR: Martes 28 de julio de 2020, 14 h, Plataforma MEET GOOGLE.

Link: meet.google.com/vod-ikcf-zzj

RESUMEN:

Catalytic enantioselection usually depends on differences in steric interactions between prochiral substrates and a chiral catalyst. We have discovered a carbene Si–H insertion in which the enantioselectivity depends primarily on the electronic characteristics of the carbene substrate, and the log(er) values are linearly related to Hammett parameters. A new class of chiral tetraphosphate dirhodium catalysts was developed; it shows excellent activity and enantioselectivity for the insertion of diarylcarbenes into the Si–H bond of silanes. Computational and mechanistic studies show how the electronic differences between the two aryls of the carbene lead to differences in energies of the diastereomeric transition states. This study provides a new strategy for asymmetric catalysis exploiting the electronic properties of the substrates.