Pd‐catalyzed bicyclization of 2‐alkynylhalobenzenes and propargylic alcohols for the formation of indeno[1,2]furans: a DFT study

Liu, Yang; Ren, Gerui; Ye, Xinchen; Que, Xianyong; Lei, Qunfang; Fang, Wenjun

doi:10.1002/poc.3271

J of Physical Organic Chem

2014

DOI: 10.1002/poc.3271

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Pd‐catalyzed bicyclization of 2‐alkynylhalobenzenes and propargylic alcohols for the formation of indeno[1,2]furans: a DFT study

Yang Liu

Gerui Ren

Xinchen Ye

et al.

Abstract: The mechanism of palladium‐catalyzed bicyclization of 2‐alkynylhalobenzenes and propargylic alcohols for the formation of indeno[1,2]furans has been studied computationally with the aid of density functional theory (DFT). Full free energy profiles are computed for different reaction equations between different reaction substrates. The calculation results showed that the catalytic cycle is found to contain six steps, oxidative addition, ligand substitution, first C ≡ C triple bond insertion, rearrangement, seco… Show more

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Cited by 3 publications

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A DFT Study on Palladium and Nickel-Catalyzed Regioselective and Stereoselective Hydrosilylation of 1,3-Disubstituted Allenes

Kuang

Wang

et al. 2017

Organometallics

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Theoretical calculations have been carried out to illustrate the mechanisms and origins of regio/stereoselective hydrosilylation of 1,3-disubstituted allenes catalyzed by Pd and Ni catalysts. Investigations indicated that the mechanisms are divided into three important steps: coordination of silane and allene to the metal center, concerted oxidative addition, and silyl/hydride migration as well as C−H/C−Si bond reductive elimination. We found that concerted oxidative addition is the rate-limiting and regioselective step for the allene-hydrosilylation reaction. Moreover, the utilization of different palladium and nickel catalysts containing N-heterocyclic carbene (NHC) ligands can lead to switchable regioselectivity in allene hydrosilylations. The reaction with Pd−NHC catalysts favors allylsilane products, whereas the reaction with Ni−NHC catalysts affords alkenylsilane products. Intrinsic electronic effects of Pd or Ni catalysts and steric repulsions between catalysts and substrates (silyl and allene) can significantly affect the regioselectivity. These computations are in accordance with observations from experiments and can help to design new palladium and nickel catalysts for the regio/stereoselectivities of allene-hydrosilylation reactions.

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A DFT Study on Palladium and Nickel-Catalyzed Regioselective and Stereoselective Hydrosilylation of 1,3-Disubstituted Allenes

Kuang

Wang

et al. 2017

Organometallics

Self Cite

View full text Add to dashboard Cite

show abstract

Mechanisms and Origins of Switchable Regioselectivity of Palladium- and Nickel-Catalyzed Allene Hydrosilylation with N-Heterocyclic Carbene Ligands: A Theoretical Study

et al. 2014

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The mechanisms and origins for the Pd- and Ni-catalyzed regioselective hydrosilylation of allene have been investigated by means of density functional theory (DFT) calculations. The free-energy profiles of Pd- and Ni-catalyzed reactions with small and bulky N-heterocyclic carbene (NHC) ligands are calculated to determine the mechanism for regioselectivities. The calculation results show that different metals (Ni vs Pd) lead to regiochemical reversals for the hydrosilylation of allene. The allylsilane is the major product via palladium catalysis with small NHC ligand, while the vinylsilane is the major product via nickel catalysis with bulky NHC ligand. Both electronic and steric factors play a key role in the regioselectivities for the hydrosilylation of allene via Pd and Ni catalysts. The calculation results are in good agreement with observed regioselectivities and could provide insights into the design of new catalysts for the regioselectivity of hydrosilylation reactions.

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Mechanisms and Reactivity Differences for Cycloaddition of Anhydride to Alkyne Catalyzed by Palladium and Nickel Catalysts: Insight from Density Functional Calculations

Sun

Ren

Cao³

2014

J. Org. Chem.

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Mechanisms and reactivity differences for the cycloaddition of anhydride to alkyne catalyzed by the palladium and nickel catalysts have been investigated by extensive density functional theory (DFT) calculations. The predicted free energy profiles for the Pd- and Ni-catalyzed reactions have been used to evaluate possible mechanisms for the formation of different products. Calculations show that the formation of isocoumarin via the decarbonylative addition of anhydride to alkyne is kinetically more favorable than the channel to indenone in the Ni-catalyzed reaction. On the contrary, the preparation of naphthalene through sequential liberation of CO2 and CO is kinetically more favorable than that the formation of indenone in the Pd-catalyzed process. The bonding differences between Pd-C and Ni-C bonds, arising from the relativistic effect of late transition metals, play an important role in regulating their catalytic activity. The calculation results show good agreement with the experiments.

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Pd‐catalyzed bicyclization of 2‐alkynylhalobenzenes and propargylic alcohols for the formation of indeno[1,2]furans: a DFT study

Cited by 3 publications

References 51 publications

A DFT Study on Palladium and Nickel-Catalyzed Regioselective and Stereoselective Hydrosilylation of 1,3-Disubstituted Allenes

A DFT Study on Palladium and Nickel-Catalyzed Regioselective and Stereoselective Hydrosilylation of 1,3-Disubstituted Allenes

Mechanisms and Origins of Switchable Regioselectivity of Palladium- and Nickel-Catalyzed Allene Hydrosilylation with N-Heterocyclic Carbene Ligands: A Theoretical Study

Mechanisms and Reactivity Differences for Cycloaddition of Anhydride to Alkyne Catalyzed by Palladium and Nickel Catalysts: Insight from Density Functional Calculations

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