Pd/IPr<sup>BIDEA</sup>-Catalyzed Hydrodefluorination of <i>gem</i>-Difluorocyclopropanes: Regioselective Synthesis of Terminal Fluoroalkenes
Huijun Qian, Zachary P. Cheng, Yani Luo, Leiyang Lv, Shuming Chen, Zhiping Li
Abstract
Developing new strategies to enable chemo- and regioselective reductions is an important topic in chemical research. Herein, an efficient and regioselective Pd/IPr BIDEA -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.