Nickel Mediated Asymmetric Allylic Alkylation Between Nitroallylic Acetates And Acyl Imidazoles

In recent years,with the rapid development of the medical field,chiral drugs have attracted more and more attention.In order to obtain a stereochemical center with a high degree of stereoselectivity,it is necessary to develop an efficient stereochemical control method,which occupies a very important position in the organic synthesis chemistry.These years,asymmetric synthesis methods have developed rapidly.However,simultaneously synthesizing chiral drugs with multiple chiral centers still composes huge challenge.Asymmetric allylic alkylation(AAA)reaction represents a well-established and important tool for organic chemistry since its discovery in the early 70 s,which allows easy access to diverse types of chiral allylic intermediates.And utlizing dual acitivation strategy,often with the assistance of acid co-catalyst,allylic alcohols are also able to undergo the asymmetric allylic alkylation reactions under mild conditions.However,the application of nitroallylic acetates in asymmetric allylic alkylation reactions has not been successfully developed,which can efficiently construct chiral nitroalkenes.Here,a nickel catalyzed asymmetric allylic alkylation reaction between imidazole-modified ketones and nitroallylic acetates is presented.This reaction is catalyzed by a simple chiral diamine-Ni(II)catalyst under mild conditions,leding to moderate to good yields of a series of enantioenriched α-allylic adducts with excellent enantioselectivities.Furthermore,transformation of the reactant allylic adducts can smoothly lead to chiral γ-nitro-esters which contain three continuous stereocenters.