DFT Study in An Asymmetric Organocatalytic Homologation: Mechanism, Origin of Stereoselectivity DOI
Yang Wang, Donghui Wei

Asian Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Окт. 24, 2024

Abstract In the present study, mechanism, origin of stereoselectivity, and role catalyst organocatalytic homologation reaction between phenyl boronate trifluoromethyl diazomethane have been theoretically investigated using density functional theory (DFT) method. Based on calculations, in situ generated ethanol plays significant triggering reaction. Moreover, [1,2]‐boron migration process is stereoselectivity‐determining step, with S ‐configured isomer being predominantly. addition, NCI analysis performed to disclose stereoselectivity.

Язык: Английский

Interplay of Ligand-Controlled Reaction Pathways: DFT Analysis of Mechanisms and Selectivities in Pd-Catalyzed Semireduction of Allenamides DOI

Ji Ma,

Simeng Qi,

Guowei Yan

и другие.

Molecular Catalysis, Год журнала: 2024, Номер 560, С. 114126 - 114126

Опубликована: Апрель 12, 2024

Язык: Английский

Процитировано

6
Theoretical investigation on cobalt-catalyzed hydroacylation reaction: Mechanism and origin of stereoselectivity DOI
Yang Wang, Han Zhang, Yue Liu

и другие.

Molecular Catalysis, Год журнала: 2022, Номер 527, С. 112410 - 112410

Опубликована: Июнь 7, 2022

Язык: Английский

Процитировано

23
Theoretical study of an N-heterocyclic carbene-catalyzed annulation reaction between an enal and a β-silyl enone: Mechanism and origin of stereoselectivity DOI
Yang Wang,

Yilu Luo,

M. Zhao

и другие.

Molecular Catalysis, Год журнала: 2023, Номер 551, С. 113621 - 113621

Опубликована: Окт. 27, 2023

Язык: Английский

Процитировано

11
Mechanistic studies on an isothiourea-catalyzed reaction of an aromatic ester with an imine DOI

Meng-Qing Yang,

Yang Wang

Molecular Catalysis, Год журнала: 2024, Номер 567, С. 114445 - 114445

Опубликована: Авг. 10, 2024

Язык: Английский

Процитировано

4
Mechanistic Insights Into the B(C6F5)3‐catalyzed Wolff Rearrangement/[2 + 2] and [4 + 2] Cascade Cyclization of α‐Diazoketones With Imines DOI

Haili Wen,

Yanshu Luo,

Yuanzhi Xia

и другие.

Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown

Опубликована: Апрель 21, 2025

Presented herein is a DFT investigation of the B(C6F5)3-catalyzed system involving Wolff rearrangement/[2 + 2] and [4 cascade cyclization α-diazoketones with imines. The study provides detailed elucidation ketene formation through B(C6F5)3-promoted rearrangement α-diazoketones, alongside substrate-dependent chemoselectivity observed in reveals three-step process, B-O adduct formation, carbene species generation via N2 extrusion facile 1,2-migration. Computational studies successfully replicate experimentally resulting intermediate different N-protected Notably, N-tert-butoxycarbonyl imines exhibit preferential stepwise [2 cyclization, while N-tert-butylcarbonyl favor concerted cycloaddition. divergence these reactions rationalized distortion/interaction analysis critical transition states.

Язык: Английский

Процитировано

0
Comparison of the Efficiency of B–O and B–C Bond Formation Pathways in Borane-Catalyzed Carbene Transfer Reactions Using α-Diazocarbonyl Precursors: A Combined Density Functional Theory and Machine Learning Study DOI Creative Commons
‬‬‬‬‬‬Kaveh Farshadfar, Kari Laasonen

ACS Catalysis, Год журнала: 2024, Номер 14(19), С. 14486 - 14496

Опубликована: Сен. 16, 2024

Lewis acidic boranes, especially tris(pentafluorophenyl)borane [B(C

Язык: Английский

Процитировано

2
Mechanism and Stereoselectivity Control of Terminal Alkyne Dimerization Activated by a Zr/Co Heterobimetallic Complex: A DFT Study DOI
Yuanyuan Sun, Jinying Zhang, Yanli Zeng

и другие.

The Journal of Organic Chemistry, Год журнала: 2023, Номер 89(1), С. 605 - 616

Опубликована: Дек. 14, 2023

Heterobimetallic complexes have recently garnered considerable attention in organic synthesis owing to their high activity and selectivity, which surpass those of monometallic complexes. In this study, the detailed mechanisms terminal alkyne dimerization activated by heterobimetallic Zr/Co complex, as well different stereoselectivities Me3SiC≡CH PhC≡CH dimerization, were investigated elucidated using density functional theory calculations. After excluding three-molecule reaction outer-sphere mechanisms, inner-sphere mechanism was determined most optimal process. The involves four processes: THF dissociation coordination first alkyne; ligand migration C–H activation; N2 insertion second reductive elimination. stereoselectivity between E-/Z- gem-isomers is C–C coupling mode two alkynes that E- Z-isomers sequence hydrogen elimination yields only an E-isomer large differences distortion interaction energies, whereas produces E-, Z-, reduced energy differences.

Язык: Английский

Процитировано

3
Kinetics of N2 Release from Diazo Compounds: A Combined Machine Learning-Density Functional Theory Study DOI Creative Commons
‬‬‬‬‬‬Kaveh Farshadfar, Arsalan Hashemi, Reza Khakpour

и другие.

ACS Omega, Год журнала: 2023, Номер 9(1), С. 1106 - 1112

Опубликована: Дек. 15, 2023

Diazo compounds are commonly employed as carbene precursors in transfer reactions during a variety of functionalization procedures. Release N2 gas from diazo may lead to formation, and the ease this process is highly dependent on characteristics substituents located vicinity moiety. A quantum mechanical density functional theory assisted by machine learning was used investigate relationship between chemical features activation energy required for elimination. Our results suggest that molecules, possessing higher positive partial charge carbon more negative terminal nitrogen, encounter lower barrier. C decreases π-donor ability lone pair π* orbital N2, while N result weak interaction vacant p carbene. The findings study can pave way molecular engineering purpose generation, which serves crucial intermediate many transformations synthetic chemistry.

Язык: Английский

Процитировано

2
DFT Mechanistic Study of the Cyclopropanation of Styrene and Aryldiazodiacetate Catalyzed by Tris(pentafluorophenyl)borane DOI Creative Commons

Xiuling Wen,

Peiquan Lu, Yong Shen

и другие.

ACS Omega, Год журнала: 2022, Номер 7(15), С. 12900 - 12909

Опубликована: Апрель 7, 2022

Metal-free boron Lewis acids, tris(pentafluorophenyl)borane B(C6F5)3, have the advantages of low toxicity and cost are a promising catalyst. A density functional theory (DFT) calculation was used to clarify mechanism origin diastereoselective cyclopropanation aryldiazodiacetate styrene derivatives catalyzed by B(C6F5)3. Four pathways were calculated: B(C6F5)3-catalyzed N-, C-, O-bound boron-activated without B(C6F5)3 catalysis. By calculating comparing energy barriers, most possible reaction proposed, that is, first, activate aryldiazodiacetate, followed removal N2 molecule, finally, nucleophilic attack occurred produce [2+1] cyclopropane products. is rate-limiting step, this step determines preference given mechanism. The calculated results in agreement with experimental observations. diastereoselectivity further explained on basis favorable steric hindrance interference between aryl group large tri(pentafluorophenyl)borane π-π stacking interaction benzene rings combined cause high diastereoselectivity, which resulted lower transition state (TS) corresponding not only provide more detailed explanation for study but also certain reference guiding significance other catalytic reactions.

Язык: Английский

Процитировано

2
DFT Study in An Asymmetric Organocatalytic Homologation: Mechanism, Origin of Stereoselectivity DOI
Yang Wang, Donghui Wei

Asian Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Окт. 24, 2024

Abstract In the present study, mechanism, origin of stereoselectivity, and role catalyst organocatalytic homologation reaction between phenyl boronate trifluoromethyl diazomethane have been theoretically investigated using density functional theory (DFT) method. Based on calculations, in situ generated ethanol plays significant triggering reaction. Moreover, [1,2]‐boron migration process is stereoselectivity‐determining step, with S ‐configured isomer being predominantly. addition, NCI analysis performed to disclose stereoselectivity.

Язык: Английский

Процитировано

0