Insights into the Synergistic Interplay of Ligand and Base Effects in Palladium-Catalyzed Enantioselectivity Hydrofunctionalization of Dienes DOI

Manzhu Zhao,

Haiyan Yuan, Jingping Zhang

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(44), P. 21031 - 21041

Published: Oct. 22, 2024

Transition-metal-catalyzed enantioselective C–O bond constructions via hydrofunctionalization involving the use of O-based nucleophiles are an important topic in synthetic chemistry. Herein, density functional theory calculations were conducted to unveil mechanism and enantioselectivity Pd-catalyzed asymmetric conjugated dienes. We found that base-assisted 4,3-activation model ligand-to-ligand hydrogen transfer (LLHT) is most preferred one among all cases, which could be ascribed favorable C–H···O interactions electrostatic interactions. For formation process, orientation substrate chiral pocket plays a significant role controlling by contributing different noncovalent On basis distortion/interaction energy decomposition analysis, distortion identified as dominant factor product chemoselectivity. BnOH acts substrate, proton shuttle, stabilizer facilitate H-transfer process both LLHT process. This study provides molecular-level insights into collaborative effect base P,N-ligand perform catalytic activity dienes, might open new avenue for designing more efficient Pd catalysis.

Language: Английский

Overlooked Ligand Role of Pyridine Substrate in Site Selectivity of Rare-Earth-Catalyzed C–H Alkylation with Alkenes DOI
Yuan Li,

Jiameng Hu,

Xinyu Tan

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 11, 2025

The rare-earth-catalyzed C-H alkylation of heteroatom-containing substrates with alkenes has been extensively studied over the past decade. Traditionally, those have regarded primarily as reactants in these reactions. In this study, mechanism 2-ethylpyridine styrene was investigated by DFT calculations, revealing often-overlooked ligand effect pyridine substrates. Our findings demonstrate that substrates, acting ligands, play a pivotal role modulating site selectivity during activation. These results enhance our understanding rare-earth catalysis and provide valuable insights into its versatile reactivity, offering novel perspective on dual roles (both reactant ligand) which are widely used functionalization

Language: Английский

Citations

0
Mechanism and Origins of Nucleophile‐Controlled Regioselectivity of Palladium‐Catalyzed Allylic C‐H Amination of 1,4‐Dienes: A Computational Study DOI
Mengyao Zhang, Shiyu Wang, Hongli Wu

et al.

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: July 23, 2024

Abstract Density functional theory calculations have been conducted to investigate the palladium‐catalyzed allylic C−H amination of 1,4‐dienes with commonly available amines. The computations indicate that reaction begins bond cleavage through concerted proton and two‐electron transfer process forge η 3 ‐allyl Pd(II) species. ensuing C−N formation was found be highly dependent on basicity nucleophile, enabling regioselectivity switch upon change nucleophile. With weakly basic aromatic amine, occurs hydrogen‐bonding enabled inner‐sphere nucleophilic attack pathway. distance between reacting carbon atom terminal is responsible for Z / E ‐selectivity. primarily due steric repulsion allyl group ligand. On other hand, outer‐sphere pathway favored more aliphatic cyclic amine. coordinating mode moiety play a crucial role in determining regioselectivity.

Language: Английский

Citations

0
Theoretical investigation on the mechanisms of palladium-catalyzed benzannulations of 1-(indol-2-yl)but-3-yn-1-ols to access to functionalized carbazoles DOI

Zitong Meng,

Kang Lv, Tao Liu

et al.

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 565, P. 114418 - 114418

Published: July 28, 2024

Language: Английский

Citations

0
Insights into the Synergistic Interplay of Ligand and Base Effects in Palladium-Catalyzed Enantioselectivity Hydrofunctionalization of Dienes DOI

Manzhu Zhao,

Haiyan Yuan, Jingping Zhang

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(44), P. 21031 - 21041

Published: Oct. 22, 2024

Transition-metal-catalyzed enantioselective C–O bond constructions via hydrofunctionalization involving the use of O-based nucleophiles are an important topic in synthetic chemistry. Herein, density functional theory calculations were conducted to unveil mechanism and enantioselectivity Pd-catalyzed asymmetric conjugated dienes. We found that base-assisted 4,3-activation model ligand-to-ligand hydrogen transfer (LLHT) is most preferred one among all cases, which could be ascribed favorable C–H···O interactions electrostatic interactions. For formation process, orientation substrate chiral pocket plays a significant role controlling by contributing different noncovalent On basis distortion/interaction energy decomposition analysis, distortion identified as dominant factor product chemoselectivity. BnOH acts substrate, proton shuttle, stabilizer facilitate H-transfer process both LLHT process. This study provides molecular-level insights into collaborative effect base P,N-ligand perform catalytic activity dienes, might open new avenue for designing more efficient Pd catalysis.

Language: Английский

Citations

0