Radical Rearrangement Of Enol Triflates And N-2-pyridin-3-yl Propan-2-yl Benzamide

The CF3 substituted carbonyl compounds are some of the most important fluorine-containing compounds.Recently,CF3 substituted carbonyl compounds have drawn special attention owing to their importance for both pharmaceutical and synthetic research.Generally,CF3 substituted carbonyl compounds are prepared from enolates or alkenes by the reactions with trifluoromethylation reagents.While many of the reported examples generally required the addition of a large excess of the trifluoromethylation reagents.These trifluoromethyl sources are either unstable or require multistep synthesis.Therefore,we have developed a new strategy for the formation of CF3 substituted carbonyl compounds through radical rearrangement of enol triflate.Isoindolinones are one of the prevalent nitrogen-containing heterocycles in natural and synthetic drug molecules.Additionally,some isoindolinone derivatives show unique biological activities.However,traditional but reliable protocols largely rely on prefunctionalized starting materials or use expensive transition metal catalysts or toxic CO gas.Therefore,we have developed a new strategy for the formation of isoindolinones through oxidative radical rearrangement of N-2-pyridin-3-yl propan-2-yl benzamide.Summary for this dissertation are as following:(1)Radical fragmentation and reconstruction of enol triflates:we have developed a facile access to synthesize a-trifluoromethyl ketones.A novel strategy for the formation of ?-CF3 ketones using enol Triflates with a catalytic amount of AgNO3/(NH4)2S2O8 has been documented.Preliminary mechanistic studies disclosed that oxidative fragmentation to release a CF3 radical from the triflyl group of enol triflate and subsequent addition of the CF3 radical to another enol triflate form the desired ?-CF3 ketones.This method utilizes readily available starting materials,is easy to handle,and features a wide substrate scope for both aromatic and aliphatic compounds.(2)Radical fragmentation and cascades of enol triflates:we have developed a facile access to ?-CF3 ketones with polycyclic.The previous work showed that oxidative fragmentation of the enol triflate release a CF3 radical from the triflyl group,which can be recycled efficiently for the subsequently radical addition to another enol triflate.Based on radical rearrangement of enol triflates,methods to the polycyclic ketones with y-CF3 substitute has been developed by cascade radical rearrangement.(3)Radical fragmentation and reconstruction of N-2-pyridin-3-yl propan-2-yl benzamide:we reported a facile access to isoindolinones.Selective C-C bond cleavage represents a powerful,straightforward strategy for constructing new organic compounds.We have developed a novel oxidative 1,2-aryl migration from carbon to nitrogen of N-2-pyridin-3-yl propan-2-yl benzamide through cleavage of C-C bond followed by 'C-C/C-N bond formation.The methods provide an efficient route for the synthesis of isoindolinone derivatives.