Copper Carbene Involved In Radical Reactions Mediated By TBHP

In the last few decades, transition metal carbenes, generated from decomposition of diazo compounds, have proved to be an efficient and widely used organic synthesis intermediates. Among these metal carbenes, Cu carbene is one of the most representative examples. Cu carbene could accomplish most transformations of metal carbenes with high selectivity. However, almost all of these transformations are ion process. Our research was focused on the radical reactions involved Cu carbene.This thesis composes with two parts as follows: 1. The Synthesis of γ-Peroxy Ester Mediated by Cu Carbene with TBHPWe developed the synthesis of γ-peroxy ester via various alkenes and ethyldiazoacetate mediated by Cu and TBHP. With the assistance of TBHP, thecyclopropantion of alkene and ethyl diazoacetate was avoided.The system has the following advantages:(1) The reaction condition is mild, and could be simply operated.(2) The system has high functional group tolerance on substrates, electronic effectand steric effect have no significant on it. 2. The Synthesis of 1,4-Dicarbonyl Compounds Mediated by Cu Carbene with TBHPWe reported the synthesis of the 1,4-dicarbonyl compounds via alkenes and Cucarbene, which is generated in situ. 1,4-Dicarbonyl compounds were generated viacombining the synthesis of γ-peroxy ester and Kornblum–De La Mare rearrangementin one pot one step.The system has the following advantages:(1) The methodology was featured by its insensitivity to moisture and air, mildconditions, and convenient operations.(2) The reaction has a wide substrate scope, a variety of functional group could betolerated under the reaction conditions.