Synthetic and Computational Studies of Acyl Radical Cyclizations with β-Alkoxyacrylates: Formal Synthesis of (±)-Longianone

2011 ◽  
Vol 64 (4) ◽  
pp. 409 ◽  
Author(s):  
Heather M. Aitken ◽  
Carl H. Schiesser ◽  
Christopher D. Donner
Keyword(s):  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Radical Cyclizations ◽  
Computational Studies ◽  
Fungal Metabolite ◽  
Acyl Radical ◽  
Functional Theory ◽  
Formal Synthesis ◽  
Acyl Radicals ◽  
Insight Into

An investigation into the cyclization of acyl radicals with mono- and disubstituted β-alkoxyacrylates is described. Ether-tethered acyl radicals, generated directly from the corresponding aldehyde, undergo cyclization to form dioxaspiro heterocyclic systems including 1,7-dioxaspiro[4,4]nonane-4,8-dione and 1,8-dioxaspiro[5,4]decane-5,9-dione. This strategy is applied to a concise formal synthesis of the fungal metabolite longianone. Density functional theory calculations provide insight into the chemistry of the acyl radicals in this study.

scholarly journals Ab Initio Study of Ferroelectric Critical Size of SnTe Low-Dimensional Nanostructures

Nanomaterials ◽  
2020 ◽  
Vol 10 (4) ◽  
pp. 732 ◽  
Author(s):  
Takahiro Shimada ◽  
Koichiro Minaguro ◽  
Tao Xu ◽  
Jie Wang ◽  
Takayuki Kitamura
Keyword(s):  
Density Functional ◽  
Critical Size ◽  
Density Functional Theory Calculations ◽  
Cell Width ◽  
Functional Theory ◽  
Unit Cells ◽  
Principle Density Functional Theory ◽  
Low Dimensional ◽  
Insight Into ◽  
Ferroelectric Perovskite

Beyond a ferroelectric critical thickness of several nanometers existed in conventional ferroelectric perovskite oxides, ferroelectricity in ultimately thin dimensions was recently discovered in SnTe monolayers. This discovery suggests the possibility that SnTe can sustain ferroelectricity during further low-dimensional miniaturization. Here, we investigate a ferroelectric critical size of low-dimensional SnTe nanostructures such as nanoribbons (1D) and nanoflakes (0D) using first-principle density-functional theory calculations. We demonstrate that the smallest (one-unit-cell width) SnTe nanoribbon can sustain ferroelectricity and there is no ferroelectric critical size in the SnTe nanoribbons. On the other hand, the SnTe nanoflakes form a vortex of polarization and lose their toroidal ferroelectricity below the surface area of 4 × 4 unit cells (about 25 Å on one side). We also reveal the atomic and electronic mechanism of the absence or presence of critical size in SnTe low-dimensional nanostructures. Our result provides an insight into intrinsic ferroelectric critical size for low-dimensional chalcogenide layered materials.

Mechanistic Insight into Construction of Axially Chiral Biaryls via Palladium/Chiral Norbornene Cooperative Catalysis: a DFT-Based Computational Study

2021 ◽  
Author(s):  
Xuexiang Ma ◽  
Aili Feng ◽  
Chengbu Liu ◽  
Dongju Zhang
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Computational Study ◽  
Density Functional Theory Calculations ◽  
Functional Theory ◽  
Cooperative Catalysis ◽  
Mechanistic Insight ◽  
Aryl Bromides ◽  
Axially Chiral ◽  
Insight Into

Density functional theory calculations were performed on a prototype of three-component reactions involving aryl iodides, 2,6-substituted aryl bromides, and acrylates to understand the construction of axially chiral biaryls through the...

On the dissolution of lithium sulfate in water: anion photoelectron spectroscopy and density functional theory calculations

2015 ◽  
Vol 17 (8) ◽  
pp. 5624-5631 ◽  
Author(s):  
Gang Feng ◽  
Gao-Lei Hou ◽  
Hong-Guang Xu ◽  
Zhen Zeng ◽  
Wei-Jun Zheng
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Photoelectron Spectroscopy ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Lithium Sulfate ◽  
Functional Theory ◽  
Anion Photoelectron Spectroscopy ◽  
Insight Into

Microscopic insight into the dissolution of Li2SO4in water was gained using photoelectron spectroscopy combined with DFT calculations.

scholarly journals A Density Functional Theory Investigation of the Reaction of Water with Ce2O-

2021 ◽  
Author(s):  
Hassan Harb ◽  
Hrant Hratchian
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Hydrogen Formation ◽  
Functional Theory ◽  
Insight Into

Cerium suboxide clusters are a recent catalyst class that has received interest for the generation of H<sub>2</sub> from water. Using density functional theory calculations, this work examines the reaction of Ce<sub>2</sub>O<sup>–</sup> clusters with H<sub>2</sub>O. It is shown that the reaction can proceed along both doublet and quartet pathways. In both cases, hydrogen formation is facilitated by intermediate structures featuring bridging hydride and hydroxide ligands. Interestingly, it is shown that metal d electrons facilitate the reduction of water. This work provides new understanding of this reaction and provides new insight into the reactivity of small lanthanide-based clusters with water.<br>

DFT insight into axial ligand effects on electronic structure and mechanistic reactivity of oxoiron(iv) porphyrin

2020 ◽  
Vol 22 (21) ◽  
pp. 12173-12179
Author(s):  
Zhifeng Ma ◽  
Naoki Nakatani ◽  
Hiroshi Fujii ◽  
Masahiko Hada
Keyword(s):  
Density Functional Theory ◽  
Electronic Structure ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Axial Ligand ◽  
Functional Theory ◽  
Ligand Effects ◽  
Insight Into

The nature of axial ligand effects is revealed by density functional theory calculations, the ability of axial ligand bound to iron is strong, and the reaction is more reactive.

Analysis of charge density in nonaaquagadolinium(III) trifluoromethanesulfonate – insight into GdIII—OH2 bonding

2020 ◽  
Vol 76 (4) ◽  
pp. 572-580
Author(s):  
Rafał Janicki ◽  
Przemysław Starynowicz
Keyword(s):  
Charge Density ◽  
Density Functional ◽  
Natural Bond Orbital ◽  
Density Functional Theory Calculations ◽  
Charge Density Distribution ◽  
Functional Theory ◽  
Topological Parameters ◽  
Covalent Contribution ◽  
Experimental Charge Density ◽  
Insight Into

The experimental charge-density distribution in [Gd(H2O)9](CF3SO3)3 has been analysed and compared with the theoretical density functional theory calculations. Although the Gd—OH2 bonds are mainly ionic, a covalent contribution is detectable when inspecting both the topological parameters of these bonds and the natural bond orbital results. This contribution originates from small electron transfer from the lone pairs of oxygen atoms to empty 5d and 6s spin orbitals of Gd3+.

New insight into the structural evolution of PbTiO3: an unbiased structure search

2017 ◽  
Vol 19 (2) ◽  
pp. 1420-1424 ◽  
Author(s):  
Cheng Lu ◽  
Jingjing Wang ◽  
Ping Wang ◽  
Xinxin Xia ◽  
Yuanyuan Jin ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Structural Evolution ◽  
Density Functional Theory Calculations ◽  
Functional Theory ◽  
Structure Search ◽  
Insight Into

The structural evolution of PbTiO3has been investigated using the CALYPSO method in combination with density functional theory calculations.

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