A convergent paired electrochemical strategy for decarboxylative C(sp<sup>2</sup>)–C(sp<sup>3</sup>) bond formation

Li, Lingjiao; Li, Zijian; Sun, Wenxuan; Li, Chao

doi:10.1039/d3qo02141f

Org. Chem. Front.

2024

DOI: 10.1039/d3qo02141f

|View full text |Cite

A convergent paired electrochemical strategy for decarboxylative C(sp²)–C(sp³) bond formation

Lingjiao Li,

Zijian Li,

Wenxuan Sun

et al.

Abstract: In this report, we describe a convergent paired electrochemical decarboxylative C(sp2)-C(sp3) cross-coupling reaction that employs readily available alkyl carboxylic acids and C(sp2)-iodides as direct coupling partners. This easy-to-operate electrochemical process...

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2024

2025

Publication Types

Select...

Article2

Relationship

Self Cite0

Independent2

Authors

Journals

Cited by 2 publications

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

DFT Investigation on Palladium-Catalyzed [2 + 2 + 1] Spiroannulation between Aryl Halides and Alkynes: Mechanism, Base Additive Role, and Solvent and Ligand Effects

Tan,

Bai,

Shi

et al. 2024

J. Phys. Chem. A

View full text Add to dashboard Cite

Transition metal-catalyzed spiroannulations are practical strategies for constructing spirocyclic skeletons of pharmaceutical and biological significance, yet the microscopic mechanism still lacks in-depth explorations. Here, the palladiumcatalyzed [2 + 2 + 1] spiroannulation between aryl halides and alkynes was studied by employing the density functional theory (DFT) method. Based on comprehensive explorations on a couple of possible reaction pathways, it is found that the reaction probably experiences C−I oxidative addition, alkyne migration insertion, Cs 2 CO 3 -assisted aryl C−H activation, C−Br bond oxidative addition, C−C coupling, arene dearomatization and reductive elimination in sequence and leads to the formation of the spiro[4,5]decane pentacyclic product (P) ultimately. Among these, the C−Br bond oxidative addition step acts as the rate-determining step (RDS) of the whole reaction, featuring a practical free energy barrier of 32.4 kcal•mol −1 at 130 °C. Computationally predicted kinetics such as half-life transferred from the RDS step's barrier on the optimal reaction pathway (1.2 × 10 1 h) coincides well with corresponding experimental results (91% yield of the spiro[4,5]decane pentacyclic product P after reacting 10 h at 130 °C). In addition, theoretical predictions regarding the solvent/ ligand effects and base additive role in the reaction, rationalized by distortion−interaction/natural population/noncovalent interaction analyses, are also in good agreement with experimental data and trend. This good agreement between experiment and theory makes sense for new designations and further experimental improvements of such Pd-catalyzed transformations.

show abstract

DFT Investigation on Palladium-Catalyzed [2 + 2 + 1] Spiroannulation between Aryl Halides and Alkynes: Mechanism, Base Additive Role, and Solvent and Ligand Effects

Tan,

Bai,

Shi

et al. 2024

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

Light-induced decarboxylative arylation of carboxylic acids via electron donor–acceptor complexes

Lei,

Tian,

et al. 2025

Org. Chem. Front.

View full text Add to dashboard Cite

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.

A convergent paired electrochemical strategy for decarboxylative C(sp²)–C(sp³) bond formation

Abstract: In this report, we describe a convergent paired electrochemical decarboxylative C(sp2)-C(sp3) cross-coupling reaction that employs readily available alkyl carboxylic acids and C(sp2)-iodides as direct coupling partners. This easy-to-operate electrochemical process...

Cited by 2 publications

References 38 publications

DFT Investigation on Palladium-Catalyzed [2 + 2 + 1] Spiroannulation between Aryl Halides and Alkynes: Mechanism, Base Additive Role, and Solvent and Ligand Effects

DFT Investigation on Palladium-Catalyzed [2 + 2 + 1] Spiroannulation between Aryl Halides and Alkynes: Mechanism, Base Additive Role, and Solvent and Ligand Effects

Light-induced decarboxylative arylation of carboxylic acids via electron donor–acceptor complexes

Contact Info

Product

Resources

About

A convergent paired electrochemical strategy for decarboxylative C(sp2)–C(sp3) bond formation

Abstract: In this report, we describe a convergent paired electrochemical decarboxylative C(sp2)-C(sp3) cross-coupling reaction that employs readily available alkyl carboxylic acids and C(sp2)-iodides as direct coupling partners. This easy-to-operate electrochemical process...

Cited by 2 publications

References 38 publications

DFT Investigation on Palladium-Catalyzed [2 + 2 + 1] Spiroannulation between Aryl Halides and Alkynes: Mechanism, Base Additive Role, and Solvent and Ligand Effects

DFT Investigation on Palladium-Catalyzed [2 + 2 + 1] Spiroannulation between Aryl Halides and Alkynes: Mechanism, Base Additive Role, and Solvent and Ligand Effects

Light-induced decarboxylative arylation of carboxylic acids via electron donor–acceptor complexes

Contact Info

Product

Resources

About

A convergent paired electrochemical strategy for decarboxylative C(sp²)–C(sp³) bond formation