Pd/IPrBIDEA-Catalyzed Hydrodefluorination of gem-Difluorocyclopropanes: Regioselective Synthesis of Terminal Fluoroalkenes
Abstract
Developing new strategies to enable chemo- and regioselective reductions is an important topic in chemical research. Herein, an efficient and regioselective Pd/IPrBIDEA-catalyzed ring-opening hydrodefluorination of gem-difluorocyclopropanes to access terminal fluoroalkenes is developed. The success of this transformation was attributed to the use of 3,3-dimethylallyl Bpin as a novel hydride donor. DFT calculations suggest that a direct 3,4'-hydride transfer via a 9-membered cyclic transition state is more favorable, which combined with the irreversibility of the reaction enables the unusual selectivity for the less thermodynamically stable terminal alkene isomer. This reaction mode is also applicable to a variety of regioselective allylic and propargyl reductions.
Repository Citation
Qian, Huijun, Zachary P. Cheng, Yani Luo, et al. 2024. "Pd/IPrBIDEA-Catalyzed Hydrodefluorination of gem-Difluorocyclopropanes: Regioselective Synthesis of Terminal Fluoroalkenes." Journal of the American Chemical Society 146(1): 24-32.
Publisher
ACS Publications
Publication Date
1-10-2024
Publication Title
Journal of the American Chemical Society
Department
Chemistry and Biochemistry
Document Type
Article
DOI
https://doi.org/10.1021/jacs.3c07992
Keywords
Anions, Hydrocarbons, Palladium, Redox reactions, Selectivity
Language
English
Format
text
