Construction of Multifunctional Complex Aromatic Compounds by HDDA Reaction

Author:Meng Xiang Zhen

Supervisor:hu yi min


Degree Year:2018





Aromatic compounds are widely found in nature,their skeleton is an important part of many natural products and synthetic organic compounds.Arynes is highly reactive intermediates and can react with a variety of substances to prepare multifunctional complex aromatic compounds.In this paper,the research progress of Arynes and HDDA reaction were reviewed.On this basis,a series of complex aromatic compounds were synthesized via Arynes intermediate produced by tetraynes.The main content includes the following three parts.1.We studied the reaction of tetraynes and α,β-unsaturated aldehydes,prepared a series of oxygenated heterocycles compounds that show a broad range of biological and pharmaceutical activities: 2H-benzopyran derivatives.We found that the [2+2] ring addition reaction from benyne and aldehyde group in the α,β-unsaturated aldehydes,the four-element heterocyclic ring-opening,molecular inner isomerization,and formation of 2H-benzopyran compounds in the mild condition.The reaction has good selectivity,wide range of substrate and high yield.2.We studied the D-A reaction of tetraynes and furan derivatives,produced a series of polycyclic aromatic hydrocarbons with oxygenated bridge.Reseaches have shown that 2,5-diphenylisobenzofuran,2,5-diphenyl furan reacted with benzyne,the yield were high,next 2,5-dimethyl furan.But the reaction of 3-acetyl-2,5-dimethylfuran and benzyne,the yield was low.3.We studied the reaction of tetraynes,amantadyl chloride and water,synthesized the amantanol esters derivatives.Accoding to the product structure,we presented the plausible mechanism.Amantadyl chloride is first react with water to form adamantinic acid,then it is the nucleophilic addition reaction of adamantane formic acid and phenyne produced by tetraynes.Because of the space effect of adamantane,the reaction has strict regional selectivity.All the new compounds obtained have been characterized by IR,NMR and HRMS Spectroscopy,some of the structure had been determined by X-ray single crystal analysis.