The Synthesis And Application Of Trifluoromethyl Propynols As Fluorine-containing Building Blocks

Organic nitrogen-,oxygen-and sulfur-containing compounds are important compounds and are widely existed in pharmaceutical molecules and natural products.They have attracted people's attention because of their special physiological activity.Meanwhile,propynol is an important structural unit in organic synthesis chemistry.Under the acid catalyst,propynol can be rearranged via Meyer-Schuster to form?,?-unsaturated carbonyl compounds which can synthesize other useful compounds.This article focuses on the hydroamination reaction of propynols,the synthesis of trifluoromethyl benzo[b]furan and benzo[b]thiophene compounds.The main contents of this thesis include:?1?The recent research of hydroamination of unsaturated hydrocarbons and the synthesis of benzofuransandbenzothiophenesarereviewed.?2?The FeCl₃/BPO-catalyzed synthesis of trifluoromethylated benzothiophenes from propynols and diaryl disulfide was developed.The low-cost and low-toxic aryl sulfide was used as the sulfur source to prepare the targeted products in moderate to excellent yield in this work.?3?A method for the Lewis acid-promoted hydroamination of propynols has been developed.In this work,trifluoromethylated propargyl alcohol undergoes a FeCl₃-catalyzed Meyer–Schuster rearrangement to produce active ketene.Then the obtained ketene proceeded the Ritter reaction with nitriles to give a nitrile onium ion intermediate,which undergo hydrolysis to furnish the N-substituted amide products.?4?A method for thecopper-catalyzedone-potsynthesisoftrifluoromethylated benzo[b]furans was developed.The recation has the merits of excellent functional groups compatibility,simple condition and don't need the expensive transition metals or ligands.