Total Synthesis Of The Bioactive Arylnaphthyl Lignan 4-O-Glycosides

1.Total synthesis of the bioactive arylnaphthyl lignan4-O-Glycosides Phyllanthusmin D,4′′-O-Acetylmananthoside B.Based on the application of phase-transfer-catalysis and Yu glycosylations,the first total syntheses of the arylnaphthyl glycosides phyllanthusmin D and4′′-O-acetylmananthoside B,which have been claimed to be ideal antitumoral lead compounds in terms of cytotoxicity,cytotoxic selectivity,and a new mechanism of action,were achieved.Starting from easily accessible compounds,the two target molecules were obtained with longest linear sequences of 9 and 15 steps,in overall yields of 29 % and 9 %,respectively.As part of this synthetic investigation,an efficient and scalable synthetic route to diphyllin was established,and the atropisomeric phenomenon in the arylnaphthyl glycosides was also confirmed。2.Complete the preliminary exploration to the total synthesis of Elsamicin AThe synthesis of the Elsamicin A glycosyl donor was completed,and the synthesis of its Chartarin was explored by several routes,meanwhile a synthetic route of gram level has been eatablished.The construction of glycoside bonds between glycosides and carbohydrates was studied by different methods,and the glycoside bonds were successfully constructed by phase transfer catalysis.In the course of exploring the construction of glycoside bonds between Chartarin and sugar,we solved the problem of poor solubility by introducing larger and soluble TBDPS group,and laying a foundation for further attempt of new glycosylation methods.