In contrast to the well-established synthetic protocols for monoalkenyl halides,a general approach to access diverse distal bisalkenyl halides with high synthetic fidelity has not yet been established,which are found ...In contrast to the well-established synthetic protocols for monoalkenyl halides,a general approach to access diverse distal bisalkenyl halides with high synthetic fidelity has not yet been established,which are found in various biologically active natural products and may also serve as useful building blocks in organic synthesis.We herein report a cobalt-catalyzed regio-and stereoselective deoxygenative hydrohalogenation of propargyl alcohols to access Z-configurated alkenyl halides and the analogous distal bisalkenyl chlorides,bromides,and iodides.Mechanistic investigation suggests that the regio-and stereoselective stepwise hydrogenation of in situ generated chloroallenes is the key step wherein the commercially available halodimethylsilane,or a surrogate combination of hydrosilane and halosilane,serves both as the hydrogen and chlorine sources.展开更多
基金Financial support from the National Natural Science Foundation of China(No.22171046)the Hundred-Talent Project of Fujian(No.50021113)the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(No.2024Z08)is gratefully acknowledged。
文摘In contrast to the well-established synthetic protocols for monoalkenyl halides,a general approach to access diverse distal bisalkenyl halides with high synthetic fidelity has not yet been established,which are found in various biologically active natural products and may also serve as useful building blocks in organic synthesis.We herein report a cobalt-catalyzed regio-and stereoselective deoxygenative hydrohalogenation of propargyl alcohols to access Z-configurated alkenyl halides and the analogous distal bisalkenyl chlorides,bromides,and iodides.Mechanistic investigation suggests that the regio-and stereoselective stepwise hydrogenation of in situ generated chloroallenes is the key step wherein the commercially available halodimethylsilane,or a surrogate combination of hydrosilane and halosilane,serves both as the hydrogen and chlorine sources.
