Work

Metalla‐Claisen Rearrangement in Gold‐Catalyzed [4+2] Reaction: A New Elementary Reaction Suggested for Future Reaction Design

Year: 2023

Type: article

Abstract: We report here computational evidence for a metalla‐Claisen rearrangement (MCR) in the case of gold‐catalyzed [4+2] cycloaddition reaction of yne‐dienes. The [4+2] reaction starts from exo cyclopropanation, followed by MCR and reductive elimination. The cyclopropane moiety formed in the first step is crucial for a low barrier of the MCR step. In addition, the importance of an appropriate combination of the tether group and the terminal substituent on alkyne in the yne‐diene substrates was studied. The mechanism of rhodium‐catalyzed [4+2] reaction of yne‐dienes was also investigated to see whether an MCR mechanism is involved or not. The findings and new understanding hereby reported represent an important advance in the catalysis field.

Source: Angewandte Chemie

DOI: 10.1002/ange.202217654

Authors: Jing Liu, Yusheng Yang, Weiming Shi, Zhi‐Xiang Yu

Institutions: Renmin University of China, Peking University, Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering, Ministry of Education

Language: English

Topic: Catalytic Alkyne Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: bronze

Funders: National Natural Science Foundation of China, Peking University

Award: 金属催化环加成反应机理研究和反应发展