DFT study on stereoselective Rh-catalyzed intramolecular [2 + 2 + 2] cycloaddition of allene–ene–ynes

Zhu, Xinrui; Fang, De‐Cai

doi:10.1039/d3qo00363a

Org. Chem. Front.

2023

DOI: 10.1039/d3qo00363a

|View full text |Cite

DFT study on stereoselective Rh-catalyzed intramolecular [2 + 2 + 2] cycloaddition of allene–ene–ynes

Xinrui Zhu

De‐Cai Fang

Abstract: Density functional theory has been employed to investigate the mechanisms of Rh-catalyzed in- tramolecular [2+2+2] cycloaddition reactions. The reaction starts with the coordination of Rh center in catalyst to alkyne...

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2023

2024

Publication Types

Select...

Article2

Relationship

Self Cite1

Independent1

Authors

Journals

Cited by 2 publications

(1 citation statement)

References 126 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…35–37 We have published the reaction mechanisms for some of the reactions in the same or similar methods, for example, M1 , 38 M6 39 and M7 . 40 We have also redone some reactions, e.g. , M3 , 41 M5 , 42 M10 43 and M11 44 with the present method.…”

mentioning

confidence: 88%

The treatment of dispersion terms for solution systems

Fang¹,

Liu²,

Liu³

et al. 2023

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

show abstract

mentioning

confidence: 88%

The treatment of dispersion terms for solution systems

Fang¹,

Liu²,

Liu³

et al. 2023

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

show abstract

Theoretical Study on the Mechanism of Ru(II)-Catalyzed Intermolecular [3 + 2] Annulation between o-Toluic Acid and 3,5-Bis(trifluoromethyl)benzaldehyde: Octahedral vs Trigonal Bipyramidal

Liu,

Fang

2024

J. Org. Chem.

View full text Add to dashboard Cite

Density functional theory was utilized to investigate the mechanism of Ru(II)-catalyzed aromatic C−H activation and addition of aromatic aldehydes. The proposed catalytic cycle consists of C−H bond activation, aldehyde carbonyl insertion for C−C coupling, lactonization for the formation of the final product, product separation, and catalyst recovery. Our calculations suggest that Ru(OAc) 2 (PCy 3 ) (referred to as CAT) is the most favorable active catalyst, facilitating the C−H bond activation to form a fivemembered ring cycloruthenium intermediate (INT2). Subsequently, the aromatic aldehyde reactant 2a enters the Ru coordination sphere, accelerating the C−C coupling and lactonization for the formation of the final product. The involvement of acetate assists in the final product separation, while INT1 re-enters the Ru coordination sphere to initiate a new catalytic cycle. Utilizing the energetic span model, the apparent activation free energy barrier was computed to be 34.3 kcal mol −1 at 443 K. Furthermore, exploration of the reaction mechanism in the absence of phosphine ligands identified Ru(OAc) 2 (p-cymene) as the most favorable active catalyst. The derived apparent activation free energy barrier offers a comprehensive explanation for the experimentally observed yields. Additionally, we have examined the disparities between the octahedral and trigonal bipyramidal structures of the catalysts concerning their effects on the reaction mechanisms and apparent activation free energy barriers.

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

DFT study on stereoselective Rh-catalyzed intramolecular [2 + 2 + 2] cycloaddition of allene–ene–ynes

Abstract: Density functional theory has been employed to investigate the mechanisms of Rh-catalyzed in- tramolecular [2+2+2] cycloaddition reactions. The reaction starts with the coordination of Rh center in catalyst to alkyne...

Cited by 2 publications

References 126 publications

The treatment of dispersion terms for solution systems

The treatment of dispersion terms for solution systems

Theoretical Study on the Mechanism of Ru(II)-Catalyzed Intermolecular [3 + 2] Annulation between o-Toluic Acid and 3,5-Bis(trifluoromethyl)benzaldehyde: Octahedral vs Trigonal Bipyramidal

Contact Info

Product

Resources

About