Origin of Regioselectivity Inversion Tuned by Substrate Electronic Properties in Co(III)‐Catalyzed Annulation of N‐Chlorobenzamide with Alkenes
Year: 2024
Type: article
Abstract: The mechanisms of Co(III)-catalyzed annulations of N-chlorobenzamide with olefins bearing different electronic properties were computationally studied and the origins of regioselectivity reversal were investigated by using energy decomposition analysis (EDA). The alkene migratory insertion step determines the regiochemistry of these reactions. EDA results indicate that the 2,1-insertion with styrene is favored because there is a weaker Pauli repulsion between the cobaltacycle Co-C σ orbital and the olefin π orbital. Conversely, the 1,2-insertion with vinyltrimethylsilane is more favorable than the 2,1-insertion. This is mostly because the increased π electron density can effectively differentiate the stabilizing electronic interactions.
Source: ChemPlusChem
Authors: Han Gao, Wujie Wang, Xiaofang Zhai, Feng Ye, Bin Liu, Gang Lu, Yuliang Li
Institutions: Shandong University, Second Hospital of Shandong University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: bronze
OpenAlex ID: W4404600550