Ni/Cu-catalyzed silylation of allylic alcohol: Theoretical studies on the mechanisms, regioselectivity, and role of ligand

Sun, Jiaying; Liu, Tao

doi:10.1016/j.mcat.2021.111456

Cited by 3 publications

(3 citation statements)

References 62 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A similar activation strategy was also reported by Liu et al in 2021, [68] wherein a Lewis acid pre-activates the alcohol hydroxyl group, allowing for oxidative addition of the weakened CÀ O bond. This particular method is based on Liu's earlier reaction for the nickel/copper-catalysed direct synthesis of allylsilanes from allyl alcohols, which exhibited a ligandcontrolled regiodivergent silylation in Figure 13.…”

Section: Ni-catalysed Cà O Activationmentioning

confidence: 65%

Recent DFT Calculations on the Mechanism of Transition‐Metal‐Catalyzed C−O Activation of Alcohols

Liu

et al. 2023

ChemCatChem

View full text Add to dashboard Cite

In recent decades, density functional theory (DFT) calculations have been extensively employed to investigate the mechanism of transition metal-catalyzed CÀ O activation reactions. These studies provide valuable insights into the structure-reactivity/ selectivity correlations via theoretical simulations and energy profile analysis. Alcohols, a category of molecules that are readily available from biomass and are low cost, represent one of the most extensively studied compounds in organic syn-thesis. In this review, we provide a brief overview of the DFT studies conducted since 2017 on the CÀ OH bond activation of alcohols catalyzed by transition metals. Specifically, the activation can be mainly divided into four categories: free radical cleavage, metal insertion, nucleophilic attack, and β-OH elimination. We will also cover some promising strategies and give a perspective regarding future research directions in this field.

show abstract

Section: Ni-catalysed Cà O Activationmentioning

confidence: 65%

Recent DFT Calculations on the Mechanism of Transition‐Metal‐Catalyzed C−O Activation of Alcohols

Liu

et al. 2023

ChemCatChem

View full text Add to dashboard Cite

show abstract

“…Then, we disclose the key factors that induce the formation of the SR -configured product as the major isomer. The widely used AIM and NCI analyses, which have been successfully utilized to recognize the predominant weak interactions, 22 are then performed to distinguish the types and strengths of the weak interactions in the stereoselective transition states (TS4RR, TS4RS, TS4SR, and TS4SS). As shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

Disclosing the mechanism and origin of stereoselectivity of the NHC-catalyzed transformation reaction of enals with acyl azolium as a key intermediate

Liang,

Shi,

Wang

2024

Catal. Sci. Technol.

View full text Add to dashboard Cite

show abstract

“…(The detailed derivation of calculated ee value is provided in Part 9 of the Supporting Information.) Then, we turn to disclose the key factors that induce the formation of RS -configured product as a major isomer. The widely used atoms-in-molecules (AIM) and non-covalent index (NCI) analyses, which have been successfully utilized to recognize the predominant weak interactions, are then performed to distinguish the types and strengths of the weak interactions in the stereoselective transition states. − …”

Section: Resultsmentioning

confidence: 99%

Mechanism and Origin of Stereoselectivity of N-Heterocyclic Carbene (NHC)-Catalyzed Transformation Reaction of Benzaldehyde with o-QDM as Key Intermediate: A DFT Study

Luo,

Zhao,

Wang

2024

J. Phys. Chem. A

View full text Add to dashboard Cite

N-heterocyclic carbene (NHC)-bound ortho-quinodimethane, served as a nucleophile, has occupied an important position for constructing various all-carbon or heterocyclic compounds and attracted increasing attention for the functionalization of benzylic carbon of aromatic aldehydes, whereas the mechanistic studies on the generation and transformations of dienolate intermediate are rare. In the present study, the mechanism of activation/transformation of aldehyde catalyzed by NHC was theoretically studied using the density functional theory (DFT) method. Based on the calculations, the nucleophilic addition process is the stereoselectivity-determining step with RSconfigured product being generated preferentially. Furthermore, non-covalent index (NCI) and atoms-in-molecules (AIM) analyses have been performed to disclose the origin of stereoselectivity, by which the larger number and stronger weak interactions are the key for stabilizing the low-energy transition state and thus leading to the stereoselectivity inducing.

show abstract

Ni/Cu-catalyzed silylation of allylic alcohol: Theoretical studies on the mechanisms, regioselectivity, and role of ligand

Cited by 3 publications

References 62 publications

Recent DFT Calculations on the Mechanism of Transition‐Metal‐Catalyzed C−O Activation of Alcohols

Recent DFT Calculations on the Mechanism of Transition‐Metal‐Catalyzed C−O Activation of Alcohols

Disclosing the mechanism and origin of stereoselectivity of the NHC-catalyzed transformation reaction of enals with acyl azolium as a key intermediate

Mechanism and Origin of Stereoselectivity of N-Heterocyclic Carbene (NHC)-Catalyzed Transformation Reaction of Benzaldehyde with o-QDM as Key Intermediate: A DFT Study

Contact Info

Product

Resources

About