Computational insights into the synergistic interplay of ligand and fluorine effects in palladium-catalyzed regiodivergent decarboxylative allylic alkylation

Wang, Shiyu; Wu, Hongli; Tang, Xiangyang; Huang, Genping

doi:10.1039/d4qo00147h

Org. Chem. Front.

2024

DOI: 10.1039/d4qo00147h

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Computational insights into the synergistic interplay of ligand and fluorine effects in palladium-catalyzed regiodivergent decarboxylative allylic alkylation

Shiyu Wang,

Hongli Wu,

Xiangyang Tang

et al.

Abstract: Palladium-catalyzed regiodivergent decarboxylative allylic alkylation of allyl difluoro-β-ketoesters provides a versatile approach to access a variety of ,-difluoroketones. In this report, density functional theory calculations have been performed to investigate...

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Cited by 2 publications

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

Meng,

Lv,

Liu

et al. 2024

Molecular Catalysis

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

Meng,

Lv,

Liu

et al. 2024

Molecular Catalysis

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

Zhao,

Yuan,

Zhang

2024

Inorg. Chem.

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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 the mechanism and enantioselectivity of Pdcatalyzed asymmetric hydrofunctionalization of conjugated dienes. We found that the base-assisted 4,3-activation model of the ligandto-ligand hydrogen transfer (LLHT) mechanism is the most preferred one among all the cases, which could be ascribed to the favorable C−H•••O interactions and the electrostatic interactions. For the enantioselective C−O bond formation process, the orientation of the substrate in the chiral pocket plays a significant role in controlling the enantioselectivity by contributing different noncovalent interactions. On the basis of the distortion/interaction model and energy decomposition analysis, the distortion energy is identified as the dominant factor controlling the product chemoselectivity. BnOH acts as the substrate, proton shuttle, and stabilizer to facilitate the H-transfer process in both LLHT and the C−O bond formation process. This study provides molecularlevel insights into the collaborative effect of the base and P,N-ligand to perform the catalytic activity in the asymmetric hydrofunctionalization of conjugated dienes, which might open a new avenue for designing more efficient base-assisted enantioselective hydrofunctionalization by Pd catalysis.

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Computational insights into the synergistic interplay of ligand and fluorine effects in palladium-catalyzed regiodivergent decarboxylative allylic alkylation

Abstract: Palladium-catalyzed regiodivergent decarboxylative allylic alkylation of allyl difluoro-β-ketoesters provides a versatile approach to access a variety of ,-difluoroketones. In this report, density functional theory calculations have been performed to investigate...

Cited by 2 publications

References 105 publications

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

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

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

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