Branch-Selective Hydromonofluoroalkylation Of 1,3-Dienes Or Alkoxyallenes

This thesis focused on development of branch-selective hydromonofluoroalkylation of 1,3-dienes or alkoxyallenes with diethyl fluoromalonate by transition metals catalysis,which provided a highly selective and atom-economical protocol for the access of value-added α-monofluoroalkylated allylic compounds.The detailed research works were as follow:1)The first asymmetric Markovnikov regioselective hydromonofluoroalkylation of 1,3-dienes with diethyl fluoromalonate was developed by using chiral Ni catalysis,which afforded a variety of value-added 4,3-Markovnikov branched-selective chiral α-monofluoroalkylated allylic molecules with excellent enantioselectives.This represented the first catalytic asymmetric hydrofluoroalkylation and Markovnikov regioselective of olefins.The features included mild condition,broad substrate scope,good functional group compatibility,easily gram scale synthesis as well as excellent enantioselectivity,and diversity transformation because of its ability to simultaneously incorporate two convertible ester groups and double bonds.The protocol was applied to the late-stage hydromonofluoroalkylation of natural products and drug molecules.2)By using diethyl fluoromalonate or bis(phenylsulfonyl)methane as monofluoroalkyl reagents,the first branch-selective hydromonofluoroalkylation of alkoxyallenes was developed,allowing the efficient and selective access of various α-monofluoroalkylated allylic ethers.This constitutes a new branch for the hydrofunctionalization of alkoxyallenes.In addition,the gram scale synthesis and diversity transformation of the products also highlighted the practicability of the method.The asymmetric variant of the current reaction was also preliminarily investigated,giving the corresponding α-monofluoroalkylated chiral allyllic ethers with moderate enantioselectivity.