Mechanistic study of the Ni-catalyzed hydroalkylation of 1,3-dienes The origins of regio- and enantioselectivities and a further rational design

Mechanistic study of the Ni-catalyzed hydroalkylation of 1,3-dienes : The origins of regio- and enantioselectivities and a further rational design

© 2023 Wiley Periodicals LLC.

Bibliographische Detailangaben
Veröffentlicht in:Journal of computational chemistry. - 1984. - 45(2024), 10 vom: 15. März, Seite 610-621
1. Verfasser: Bai, Yuna (VerfasserIn)
Weitere Verfasser: Xian, Anmei, Yang, Xing, Zhou, Ming, Zhao, Xuefei, Zhao, Lili
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2024
Zugriff auf das übergeordnete Werk:Journal of computational chemistry
Schlagworte:Journal Article enantioselectivity hydroalkylation ligand design reaction mechanism regioselectivity
Beschreibung
Zusammenfassung:© 2023 Wiley Periodicals LLC.
The development of the catalytic regio- and enantioselective hydrofunctionalization of 1,3-dienes remains a challenge and requires deep insight into the reaction mechanisms. We herein thoroughly studied the reaction mechanism of the Ni-catalyzed hydroalkylation of 1,3-dienes with ketones by density functional theory (DFT) calculations. It reveals that the reaction is initiated by stepwise oxidative addition of EtO-H followed by 1,3-diene migratory insertion to generate the alkylnickel(II) intermediate, rather than the experimentally proposed ligand-to-ligand hydrogen transfer (LLHT) mechanism. In addition, we rationalized the role of t BuOK in the subsequent addition of enolate of ketone and transmetalation process. Based on the whole catalysis, the CC reductive elimination step, turns out to be the rate- and enantioselectivity-determining step. Furthermore, we disclosed the origins of the regio- and enantioselectivity of the product, and found that the 1,2-selectivity lies in the combination effects of the ligand-substrate electrostatic interactions, orbital interactions and Pauli repulsions, while the enantioselectivity mainly arises from substrate-ligand steric repulsions. Based on mechanistic study, new biaryl bisphosphine ligands affording higher enantioselectivity were designed, which will help to improve current catalytic systems and develop new transition-metal-catalyzed hydroalkylations
Beschreibung:Date Revised 01.03.2024
published: Print-Electronic
Citation Status PubMed-not-MEDLINE
ISSN:1096-987X
DOI:10.1002/jcc.27277