Theoretical Studies on the Reaction Mechanism for the Cycloaddition of Zwitterionic π-Allenyl Palladium Species: Substrate-Controlled Isomerization

Year: 2024

Type: article

Abstract: Zwitterionic π-allenyl palladium species are newly developed intermediates. A substrate-controlled step existed in the cycloaddition of zwitterionic π-allenyl palladium species with tropsulfimides or tropones. With the assistance of previously experimental studies, zwitterionic allenyl/propargyl palladium species was provenly found by HRMS. Further DFT calculation studies show that zwitterionic π-allenyl palladium species are generated through the oxidative addition of Pd(0), which can be promoted by Lewis acid like Yb(OTf)3, and the cycloaddition more likely undergoes through an outer sphere nucleophilic attack. The isomerization is caused by the difference of dissociation energy between the cycloaddition intermediation of tropsulfimides and tropones, forming the substrate-controlled specificity.

Source: Molecules

DOI: 10.3390/molecules30010103

Authors: Yongjie Long, Jiahao Shen, Min Shi, Yin Wei

Institutions: Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, State Key Laboratory of Organometallic Chemistry

Language: English

Topic: Catalytic Cross-Coupling Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: gold

Estimated APC paid: $3,069

Funders: National Natural Science Foundation of China, National Key Research and Development Program of China, Fundamental Research Funds for the Central Universities

OpenAlex ID: W4405949560