Copper Catalyzed Defluoroalkylation To Synthesis Monofluoroallenes

Allenes are uniquely useful intermediates in organic synthesis because their structure and reactivity properties complement the chemistry of alkenes and alkynes in many cases,and allene structures are also found in many natural products as well as pharmaceutical-related compounds.Fluorine has special physicochemical properties due to its strong electron-withdrawing properties and relatively small atomic radius.Various types of fluorinated moieties often exhibit distinct reactivities when introduced into different organic compounds,increasing the need for practical methods for the synthesis of fluorine-containing groups.In view of the wide application of allene compounds,axially chiral monofluoroallenes will have great potential in drug discovery and new material development in the future.Therefore,it is very necessary to develop a facile method for the synthesis of f monofluoroallenes.In this work,a novel copper/carbene ligand asymmetric catalytic system was developed to obtain axially chiral monofluoroallene products in high yields and high ee values.The main results are as follows:1.The substrate has a wide range of universality,and when the catalyst is reduced to 1 mol% and the reaction is expanded to 1 mmol,there is still a high yield and ee value,which can be prepared on a large scale;2.Modification of natural products to synthesize some monofluoroallenes containing natural product skeletons,which further expands the application scope of our reaction system;3.Fluorine-containing β-allenols products can be easily obtained by using our catalytic synthesis system.β-allenols is a kind of very important synthetic intermediate in organic synthesis,and we have successfully realized the cyclization ofβ-allenols in the exploration of derivatization and fluorine-containing derivative synthesis of active drug molecules.