Pd(0)-Catalyzed Intramolecular Reductive Heck Reaction Of Vinyl Iodide And Oxime Ether

The Heck reaction is one of the most important carbon-carbon bondforming reactions in organic chemistry,it has been developed for more than 30 years.In recently,great achievements have been made in the field of Heck reactions,especially the asymmetric Heck reactions.Realized from intermolecular to intramolecular,racemization to optical rotation.The asymmetric Heck reactions have been developed and widely used in the synthesis of natural products,drug molecules and materials.Although there are obstacles to the elimination of β-H in the synthesis of target products to obtain achiral products,there are many strategies to solve them.While the intramolecular reductive Heck reaction of aryl/vinyl halide and alkene has been extensively investigated,the asymmetric Reductive Heck Reactions of oxime ether has not been realized so far.The paper reports the Pd(0)-catalyzed intramolecular reductive Heck reaction of vinyl iodide and oxime ether with the use of formic acid as the reductant.It is found that TsOH additive plays a crucial role on the reaction efficiency and SEGPhos ligand enables cyclic allylic N-alkoxy amine products with high enantioselectivity,and we the 5-substituted 3-aminopiperidines could be synthesized under milder conditions.3-aminopiperidines are one of the most important saturated heterocycles,which are ubiquitous in biologically active synthetic chemicals and natural products.Therefore,the asymmetric reductive Heck reaction has a good application prospect.