Synthesis Of Macrocyclic Compounds Containing Tetrabenzocyclooctatetetraene As A Backbone And Containing A Chiral Molecular Knot

This thesis mainly focuses on the synthesis of the chiral molecular knot containing macrocyclic compound based on “saddle-shaped” tetraphenylene skeleton,for possible application in the field of molecular recognition as well as catalysis.The molecular knot in this macrocyclic compound features two aliphatic chains,which contribute two important functions to the whole molecular design: One is to generate a special cavity with the tetraphenylene part,enabling recognition of variety of guest molecule with different sizes;Another one is to introduce chirality to the molecule for chiral recognition.In consideration of the lack of efficient methods to construct a molecular knot on the tetraphenylene framework as well as the difficulty to synthesize tetraphenylene derivatives,we studied the synthesis of tetraphenylene macrocycles in two steps:In the first step,with purpose of accumulating relevant experience,we studied the synthesis of mono-chain compound first.After exploring the relationship between the yield and the length of aliphatic chain in the RCM reaction,chiral separation of the racemic mixtures of compound 128,129,130,131 was achieved for the determination of their absolute configuration.In the next step,we studied the synthesis of the double-chain compound.We adopted the strategy of stepwise construction of the two crossing aliphatic chains in the molecular knot after a carefully planned synthetic route design.First,bromo substituents were introduced to the 3,11-position of 2,10-dihydroxytetraphenylene.Subsequently,the first chain was built via a RCM reaction between two carbon chains.After converting the bromine atoms at 3,11-position to hydroxyl groups,the second chain across the top of the first one was built in a similar way.Ultimately,the double-chain compound 140 was achieved in 13 synthetic steps in a reliable manner.Compound 140's possible configuration was also studied by variable temperature NOESY 2D spectroscopy.