DFT Study on the Mechanisms and Selectivities in Rh (III)-Catalyzed [5 + 1] Annulation of 2-Alkenylanilides and 2-Alkylphenols with Allenyl Acetates DOI

Ji Ma,

Simeng Qi,

Guowei Yan

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(12), P. 8562 - 8577

Published: June 7, 2024

The mechanisms and regio-, chemo-, stereoselectivity were theoretically investigated in the Rh(III)-catalyzed [5 + 1] annulation of 2-alkenylanilides 2-alkylphenols with allenyl acetates. Two different reactants, 2-alkylphenols, selected as model systems density functional theory calculations. obtained theoretical results show that both these reactants exhibit similar steps, namely, (1) N-H/O-H deprotonation C-H activation, (2) acetate migratory insertion, (3) β-oxygen elimination, (4) intramolecular nucleophilic addition nitrogen/oxygen-rhodium bond resulting 1]-annulation, (5) protonation formation desired product regeneration Rh(III) catalyst. evidence suggests selectivity is determined at step acetate's insertion. Moreover, regioselectivity driven by electronic effects, while interaction energies (C-H···π C-H···O interactions) play a more imperative role controlling stereoselectivity. not only well rationalize experimental observations but also provide important mechanistic insights for related types 1]-annulation reactions.

Language: Английский

Stereoselective Photoredox Catalyzed (3+3) Dipolar Cycloaddition of Nitrone with Aryl Cyclopropane DOI
Yao Xu, Haixiang Gao,

Chengkai Pan

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 13, 2023

Abstract By resorting to the principle of remote activation, we herein demonstrate first photoredox catalyzed (3+3) dipolar cycloaddition nitrones with aryl cyclopropanes. Key fidelity reaction resides in a facile manner substrate activation by single‐electron transfer (SET) oxidation catalysis, and takes place through stepwise cascade encompassing three‐electron‐type nucleophilic substitution triggered cyclopropane ring‐opening diastereoselective 6‐endo‐ trig radical cyclization manifold. The proceeds under mild conditions excellent regio‐ stereoselectivity, nicely complementing well‐developed Lewis acid donor‐acceptor Other merits protocol include wide scope cyclopropanes diversified patterns good functional‐group compatibility. A mechanism involving an cation promoted mode was also proposed supported mechanistic experiments.

Language: Английский

Citations

25
Advances in organocatalytic asymmetric [3 + 3] cycloadditions: synthesis of chiral six-membered (hetero)cyclic compounds DOI

Ziqi Zhu,

Tian‐Zhen Li,

Sijia Liu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(19), P. 5573 - 5604

Published: Jan. 1, 2024

This review has summarized the development of organocatalytic asymmetric [3 + 3] cycloadditions and given insights into remaining challenges to promote future this field.

Language: Английский

Citations

18
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

et al.

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 560, P. 114126 - 114126

Published: April 12, 2024

Language: Английский

Citations

6
Mechanistic insights and stereoselectivity in Ni(II)-catalyzed asymmetric [3 + 2]/[3 + 3] cycloaddition reactions of donor-acceptor cyclopropanes: A DFT study DOI
Jie Fan, Ran Fang,

Yanyun Dong

et al.

Molecular Catalysis, Journal Year: 2025, Volume and Issue: 579, P. 115034 - 115034

Published: March 24, 2025

Language: Английский

Citations

0
Stereoselective Photoredox Catalyzed (3+3) Dipolar Cycloaddition of Nitrone with Aryl Cyclopropane DOI
Yao Xu, Haixiang Gao,

Chengkai Pan

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(44)

Published: Sept. 13, 2023

Abstract By resorting to the principle of remote activation, we herein demonstrate first photoredox catalyzed (3+3) dipolar cycloaddition nitrones with aryl cyclopropanes. Key fidelity reaction resides in a facile manner substrate activation by single‐electron transfer (SET) oxidation catalysis, and takes place through stepwise cascade encompassing three‐electron‐type nucleophilic substitution triggered cyclopropane ring‐opening diastereoselective 6‐endo‐ trig radical cyclization manifold. The proceeds under mild conditions excellent regio‐ stereoselectivity, nicely complementing well‐developed Lewis acid donor‐acceptor Other merits protocol include wide scope cyclopropanes diversified patterns good functional‐group compatibility. A mechanism involving an cation promoted mode was also proposed supported mechanistic experiments.

Language: Английский

Citations

5
Theoretical Analysis of a Three-Component Reaction between Two Diazo Compounds and a Hydroxylamine Derivative: Mechanism, Enantioselectivity, and Effect of Cooperative Catalysis DOI

Simeng Qi,

Ji Ma,

Guowei Yan

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(24), P. 17215 - 17226

Published: Nov. 30, 2023

The mechanism, enantioselectivity, and effect of chiral phosphoric acid (CPA) cocatalyst were investigated by the density functional theory (DFT) for three-component asymmetric aminohydroxylation between two diazo compounds a hydroxylamine derivative. This type cascade process is cooperatively catalyzed Rh2(OAc)4 CPA. obtained results clearly indicate that first step global reaction involves nucleophilic attack at nitrogen center N-hydroxyaniline rhodium-carbene intermediates producing imines. Subsequently, an enolate intermediate was recognized as key species generated from second compound leaving benzyl alcohol (BnOH) fragment in presence same dirhodium catalyst. Then, terminated Mannich-type addition, delivering products S-R conformation with assistance acid. distortion/interaction analysis shows relative distortions CPA enol play vital role energy ordering stereocontrolling transition states (TSs). Furthermore, influence different substituents fully rationalized analysis. study opens up novel synthetic possibilities improves predictability when exploring related types organic transformations.

Language: Английский

Citations

5
DFT Study on the Mechanism of Phosphine-Catalyzed Ring-Opening Reaction of Cyclopropyl Ketone DOI
Xiaohan Yu, Yang Wang

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

In the present study, mechanism, origin of chemoselectivity, and substituent effects phosphine-catalyzed ring-opening reaction cyclopropyl ketone have been investigated using DFT method. Multiple pathways, including formation hydrofluorenone, Cloke-Wilson product, cyclopenta-fused were studied compared. The computational results show that pathway for hydrofluorenone is most favorable one, which involves four processes: nucleophilic substitution to open three-membered ring, an intramolecular Michael addition enolate intermediate, [1,5]-proton transfer give ylide, Wittig deliver final product. For disclosing structural analysis local reactivity index performed. Moreover, also considered QTAIM analysis. current study would provide useful insights understanding chemoselective reactions.

Language: Английский

Citations

1
Mechanistic Insights into the Ligand-Directed Divergent Synthesis of 2-Benzazepine Derivatives via Ni-Catalyzed Tunable Cyclization/Cross-Coupling: A DFT Study DOI
Tao Liu,

Zitong Meng,

Yihang Zhou

et al.

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(43), P. 17946 - 17953

Published: Oct. 18, 2023

The detailed mechanisms of Ni-catalyzed ligand-controlled cyclization/cross-coupling o-bromobenzenesulfonyl acrylamide (1a) with trifluoromethyl alkene were investigated by DFT calculations. computational results support a single-electron reduction NiII precatalyst to give BrNiIL species, which would react 1a via oxidative addition afford the (Ar)NiIIILBr2 complex. subsequent cyclizations did not proceed until was reduced key (Ar)NiIL For bpy-involving reaction, steps include nucleophilic attack carbonyl carbon atom, N-C bond breaking, intramolecular migratory insertion, as well concerted C-C cross-coupling and β-F elimination. While ligand terpyridine promotes 7-endocyclization followed stepwise insertion elimination 2-benzazepine 2,5-dione. both reactions, theoretical study implied that most favorable mechanism involved NiI-NiIII-NiI catalytic cycle. origins chemoselectivity, coupled factors responsible, addressed.

Language: Английский

Citations

1
DFT Study on the Mechanisms and Selectivities in Rh (III)-Catalyzed [5 + 1] Annulation of 2-Alkenylanilides and 2-Alkylphenols with Allenyl Acetates DOI

Ji Ma,

Simeng Qi,

Guowei Yan

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(12), P. 8562 - 8577

Published: June 7, 2024

The mechanisms and regio-, chemo-, stereoselectivity were theoretically investigated in the Rh(III)-catalyzed [5 + 1] annulation of 2-alkenylanilides 2-alkylphenols with allenyl acetates. Two different reactants, 2-alkylphenols, selected as model systems density functional theory calculations. obtained theoretical results show that both these reactants exhibit similar steps, namely, (1) N-H/O-H deprotonation C-H activation, (2) acetate migratory insertion, (3) β-oxygen elimination, (4) intramolecular nucleophilic addition nitrogen/oxygen-rhodium bond resulting 1]-annulation, (5) protonation formation desired product regeneration Rh(III) catalyst. evidence suggests selectivity is determined at step acetate's insertion. Moreover, regioselectivity driven by electronic effects, while interaction energies (C-H···π C-H···O interactions) play a more imperative role controlling stereoselectivity. not only well rationalize experimental observations but also provide important mechanistic insights for related types 1]-annulation reactions.

Language: Английский

Citations

0