Density Functional Theory Studies of Negishi Alkyl–Alkyl Cross-Coupling Reactions Catalyzed by a Methylterpyridyl-Ni(I) Complex

2008 ◽  
Vol 73 (10) ◽  
pp. 3680-3688 ◽  
Author(s):  
Xufeng Lin ◽  
David Lee Phillips
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Functional Theory ◽  
Cross Coupling Reactions

scholarly journals Radical Coupling Reactions of Hydroxystilbene Glucosides and Coniferyl Alcohol: A Density Functional Theory Study

2021 ◽  
Vol 12 ◽  
Author(s):  
Thomas Elder ◽  
Jorge Rencoret ◽  
José C. del Río ◽  
Hoon Kim ◽  
John Ralph
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Biosynthetic Pathway ◽  
Cross Coupling ◽  
Coniferyl Alcohol ◽  
Coupling Reactions ◽  
Functional Theory ◽  
Radical Coupling ◽  
Synthetic Models

The monolignols, p-coumaryl, coniferyl, and sinapyl alcohol, arise from the general phenylpropanoid biosynthetic pathway. Increasingly, however, authentic lignin monomers derived from outside this process are being identified and found to be fully incorporated into the lignin polymer. Among them, hydroxystilbene glucosides, which are produced through a hybrid process that combines the phenylpropanoid and acetate/malonate pathways, have been experimentally detected in the bark lignin of Norway spruce (Picea abies). Several interunit linkages have been identified and proposed to occur through homo-coupling of the hydroxystilbene glucosides and their cross-coupling with coniferyl alcohol. In the current work, the thermodynamics of these coupling modes and subsequent rearomatization reactions have been evaluated by the application of density functional theory (DFT) calculations. The objective of this paper is to determine favorable coupling and cross-coupling modes to help explain the experimental observations and attempt to predict other favorable pathways that might be further elucidated via in vitro polymerization aided by synthetic models and detailed structural studies.

scholarly journals Nickel versus Palladium in Cross-Coupling Catalysis: On the Role of Substrate Coordination to Zerovalent Metal Complexes

Synthesis ◽  
2019 ◽  
Vol 52 (04) ◽  
pp. 565-573 ◽  
Author(s):  
Alasdair K. Cooper ◽  
Paul M. Burton ◽  
David J. Nelson
Keyword(s):  
Functional Groups ◽  
Density Functional ◽  
Aryl Halide ◽  
Cross Coupling ◽  
Density Functional Theory Calculations ◽  
Detailed Comparison ◽  
Coupling Reactions ◽  
Functional Theory ◽  
Cross Coupling Reactions

A detailed comparison of the effect of coordinating functional groups on the performance of Suzuki–Miyaura reactions catalysed by nickel and palladium is reported, using competition experiments, robustness screening, and density functional theory calculations. Nickel can interact with a variety of functional groups, which manifests as selectivity in competitive cross-coupling reactions. The presence of these functional groups on exogenous additives has effects on cross-coupling reactions that range from a slight improvement in yield to the complete cessation of the reaction. In contrast, palladium does not interact sufficiently strongly with these functional groups to induce selectivity in cross-coupling reactions; the selectivity of palladium-catalysed cross-coupling reactions is predominantly governed by aryl halide electronic properties.

scholarly journals DFT Study of Unstrained Ketone C-C Bond Activation via Rhodium(I)-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions

2019 ◽  
Author(s):  
Dengmengfei Xiao ◽  
Lili Zhao ◽  
Diego Andrada
Keyword(s):  
Density Functional ◽  
Bond Activation ◽  
Chemical Reactivity ◽  
Cross Coupling ◽  
Underlying Mechanism ◽  
Reductive Elimination ◽  
Coupling Reactions ◽  
Co Catalysts ◽  
Cross Coupling Reactions ◽  
Strain Model

Unstrained cyclic ketones can participate in cooperative Suzuki-Miyaura cross-coupling type reaction using rhodium(I)-based catalyst via C-C bond activation. The regioselectivity indicates a trend where the most substituted side is activated and it is controlled by the beta-substituents. In this work, Density Functional Theory (DFT) calculations have been carried out to disclose the underlying mechanism in the reaction of a ketone series and arylboronate using ylidene as ancillary ligand and pyridine as co-catalysts. The computed energies suggest the reductive elimination step with the highest energy while the reductive elimination has the highest energy barrier. By the means of the Activation Strain Model (ASM) of chemical reactivity, it is found that the ketone strain energy released on the oxidative addition does not control the relativity of the OA reactivity, but indeed is the interaction energy between Rh(I) and C-C bond the ruling effect. The effect of the beta-substituents on regioselectivity has been additionally studied.

scholarly journals A novel selective fluorescent chemosensor for Fe3+ ions based on phthalonitrile dimer: synthesis, analysis, and theoretical studies

2020 ◽  
Vol 44 (5) ◽  
pp. 1254-1264
Author(s):  
Shaya AL-RAQA ◽  
İpek ÖMEROĞLU ◽  
Doğan ERBAHAR ◽  
Mahmut DURMUŞ
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Interaction Mechanism ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Density Functional Theory Calculations ◽  
Theoretical Studies ◽  
Functional Theory ◽  
Cross Coupling Reaction ◽  
Ft Ir

Phenyl-4,4-di(3,6-dibutoxyphthalonitrile) (3) was synthesized by the reaction of 1,4-phenylenebisboronic acid (1) and 4-bromo-3,6-dibutoxyphthalonitrile (2), using Suzuki cross-coupling reaction. The newly synthesized compound (3) was characterized by FT-IR, MALDI-MS, ESI-MS, 1H-NMR, 13C-NMR, and 13C-DEPT-135-NMR. The fluorescence property of phenyl-4,4-di(3,6- dibutoxyphthalonitrile) (3) towards various metal ions was investigated by fluorescence spectroscopy, and it was observed thatthe compound (3) displayed a significantly ‘turn-off’ response to Fe3+, which was referred to 1:2 complex formation between ligand (3) and Fe3+. The compound was also studied via density functional theory calculations revealing the interaction mechanism of the molecule with Fe3+ ions.

scholarly journals Radical coupling reactions of piceatannol and monolignols: A density functional theory study

2019 ◽  
Vol 164 ◽  
pp. 12-23 ◽  
Author(s):  
Thomas Elder ◽  
José Carlos del Río ◽  
John Ralph ◽  
Jorge Rencoret ◽  
Hoon Kim ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Coupling Reactions ◽  
Density Functional Theory Study ◽  
Functional Theory ◽  
Radical Coupling

Radical Coupling Reactions in Lignin Synthesis: A Density Functional Theory Study

2012 ◽  
Vol 116 (16) ◽  
pp. 4760-4768 ◽  
Author(s):  
Amandeep K. Sangha ◽  
Jerry M. Parks ◽  
Robert F. Standaert ◽  
Angela Ziebell ◽  
Mark Davis ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Coupling Reactions ◽  
Density Functional Theory Study ◽  
Functional Theory ◽  
Radical Coupling ◽  
Lignin Synthesis
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