The Origin of Catalysis and Regioselectivity of Lewis Acid‐Catalyzed Diels‐Alder Reactions with Tropone** DOI Creative Commons
Eveline H. Tiekink, Pascal Vermeeren, Trevor A. Hamlin

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(39)

Published: April 20, 2023

We have studied the uncatalyzed and Lewis acid (LA)-catalyzed cycloaddition reaction between tropone 1,1-dimethoxyethene using dispersion-corrected relativistic density functional theory (DFT). The LA catalysts BF3 , B(C6 H5 )3 F5 efficiently accelerate both competing [4+2] [8+2] reactions by lowering activation barrier up to 12 kcal mol-1 compared reaction. Our study reveals that catalyst promotes pathways LUMO-lowering catalysis demonstrates Pauli-lowering is not always operative catalytic mechanism in reactions. Judicious choice of can effectively impart regiocontrol cycloaddition: furnishes adduct while yields adduct. discovered regioselectivity shift finds its origin ability absorb distortion adopting a trigonal pyramidal geometry around boron atom.

Language: Английский

A Combined DFT, Energy Decomposition, and Data Analysis Approach to Investigate the Relationship Between Noncovalent Interactions and Selectivity in a Flexible DABCOnium/Chiral Anion Catalyst System DOI
E. F. Miller, Binh Khanh, Jacquelyne A. Read

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(19), P. 12369 - 12385

Published: Sept. 27, 2022

Developing strategies to study reactivity and selectivity in flexible catalyst systems has become an important topic of research. Herein, we report a combined experimental computational aimed at understanding the mechanistic role achiral DABCOnium cofactor regio- enantiodivergent bromocyclization reaction. It was found that electron-deficient aryl substituents enable rigidified transition states via anion−π interaction with catalyst, which drives In contrast, electron-rich groups on result significantly more states, where interactions between substrate are important. An analysis not only lowest-energy state structures but also ensemble low-energy conformers energy decomposition machine learning crucial revealing dominant noncovalent responsible for observed changes this system.

Language: Английский

Citations

14
Copper-catalyzed and biphosphine ligand controlled 3,4-boracarboxylation of 1,3-dienes with carbon dioxide DOI

He Yao,

Wenhao Ji,

Yi Feng

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 110076 - 110076

Published: May 1, 2024

Language: Английский

Citations

2
Recent Advances in Copper‐Catalyzed Carboxylation Reactions with CO2 DOI
Yu‐Fei Song, Yu Zhang, Zhengkai Chen

et al.

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(7)

Published: June 8, 2022

Abstract As an ideal one‐carbon synthon, CO 2 has been successfully utilized in diverse carboxylation reactions to construct a series of value‐added products. Among various transition‐metal catalysts, the inexpensive copper complexes exhibit unique catalytic activity reactions. This review summarizes recent developments copper‐catalyzed with , contents which are divided into five parts based on type substrates or products: organic halides and their surrogates, C−C double bonds, triple C−H bonds synthesis heterocycles.

Language: Английский

Citations

8
Mechanism of Co(iii)-catalyzed annulation of N-chlorobenzamide with styrene and origin of cyclopentadienyl ligand-controlled enantioselectivity DOI
Han Gao, Wujie Wang, Xiangying Lv

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(7), P. 1643 - 1650

Published: Jan. 1, 2023

The additional substituents on BINOL-Cp ligands exert great influence both the geometries of styrene insertion transition states and major factors controlling enantioselectivity.

Language: Английский

Citations

4
Computational insights into strain-increase allylborations for alkylidenecyclopropanes DOI

Lingfei Hu,

Han Gao, Yanlei Hu

et al.

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(50), P. 7034 - 7037

Published: Jan. 1, 2022

The origins of the reactivity strain-increase allylborations were computationally investigated. low vinylcyclopropyl boronates is due to weak electronic interactions between benzaldehyde and allylboronates. By increasing acidity boron center, significantly improved because stronger stabilizing O→B interaction effectively compensates for destabilizing steric effects.

Language: Английский

Citations

6
Nickel/Brønsted acid dual-catalyzed regioselective C–H bond allylation of phenols with 1,3-dienes DOI
Jiao Long, Chao Ding,

Guoyin Yin

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(14), P. 3834 - 3839

Published: Jan. 1, 2022

A nickel/Brønsted acid dual-catalyzed C-H bond ortho -allylation of phenols with 1,3-dienes has been developed. This methodology is readily applicable to the modification complex pharmaceutical molecules.

Language: Английский

Citations

6
How Ionization Catalyzes Diels‐Alder Reactions DOI Creative Commons
Pascal Vermeeren, Trevor A. Hamlin, F. Matthias Bickelhaupt

et al.

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(40)

Published: April 20, 2022

The catalytic effect of ionization on the Diels-Alder reaction between 1,3-butadiene and acrylaldehyde has been studied using relativistic density functional theory (DFT). Removal an electron from dienophile, acrylaldehyde, significantly accelerates shifts mechanism concerted asynchronous for neutral to stepwise radical-cation reaction. Our detailed activation strain Kohn-Sham molecular orbital analyses reveal how dienophile enhances reactivity via two mechanisms: (i) by amplifying asymmetry in dienophile's occupied π-orbitals such extent that goes thus with substantially less steric (Pauli) repulsion per step; (ii) enhancing stabilizing interactions result ability singly engage additional three-electron bonding interaction highest diene.

Language: Английский

Citations

5
Mechanism and Origins of Diastereo‐ and Regioselectivities of Palladium‐Catalyzed Remote Diborylative Cyclization of Dienes via Chain‐Walking Strategy DOI
Shuqi Kong, Mengyao Zhang, Shiyu Wang

et al.

Chemistry - An Asian Journal, Journal Year: 2022, Volume and Issue: 18(1)

Published: Nov. 23, 2022

Density functional theory calculations have been performed to investigate the palladium-catalyzed remote diborylative cyclization of dienes. The computations reveal that reaction proceeds through a rarely explored Pd(II)/Pd(IV) catalytic cycle, and formal σ-bond metathesis between alkylpalladium intermediate B2 pin2 occurs via pathway B-B oxidative addition/C-B reductive elimination involving high-valent Pd(IV) species. diastereoselectivity is determined by migratory insertion into Pd-C bond, which mainly due combination torsional strain effect, steric repulsion C-H-O hydrogen-bonding interaction. hindrance around reacting carbon group in C-B turns out be key factor provide driving force chain walking Pd center terminal primary position, enabling experimentally observed regioselectivity.

Language: Английский

Citations

4
Mechanistic insight into the ligand-controlled regioselective hydrocarboxylation of aryl olefins with palladium catalyst: A computational study DOI

Fengyue Zhao,

Lingli Han,

Tao Liu

et al.

Journal of Organometallic Chemistry, Journal Year: 2023, Volume and Issue: 989, P. 122645 - 122645

Published: Feb. 15, 2023

Language: Английский

Citations

0
The Origin of Catalysis and Regioselectivity of Lewis Acid‐Catalyzed Diels‐Alder Reactions with Tropone** DOI Creative Commons
Eveline H. Tiekink, Pascal Vermeeren, Trevor A. Hamlin

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(39)

Published: April 20, 2023

We have studied the uncatalyzed and Lewis acid (LA)-catalyzed cycloaddition reaction between tropone 1,1-dimethoxyethene using dispersion-corrected relativistic density functional theory (DFT). The LA catalysts BF3 , B(C6 H5 )3 F5 efficiently accelerate both competing [4+2] [8+2] reactions by lowering activation barrier up to 12 kcal mol-1 compared reaction. Our study reveals that catalyst promotes pathways LUMO-lowering catalysis demonstrates Pauli-lowering is not always operative catalytic mechanism in reactions. Judicious choice of can effectively impart regiocontrol cycloaddition: furnishes adduct while yields adduct. discovered regioselectivity shift finds its origin ability absorb distortion adopting a trigonal pyramidal geometry around boron atom.

Language: Английский

Citations

0