Synthesis And Properties Of C₂-symmetric Biheterocycle-fused 1,1'-binaphthyl-2,2'-diols

Heterocycle-fused aromatic compounds based on chiral binaphthol skeleton have been widely used in the field of molecular recognition and asymmetric synthesis.In addition,binaphthols are also widely used in the field of organic optoelectronic materials due to their conjugated structure.In view of the potential applications of heterocyclic fused aromatic compounds in the fields of chiral recognition and asymmetric catalysis,a series of C₂-symmetric heterocycle-fused binaphthols were designed and synthesized in this thesis.These noval chiral binaphthols are completed by well-defined synthetic routes by introducing various heterocycles at 5,5',6,6'-positions of binaphthols.Hence,heterocycles such as indole,oxadiazole,thiadiazole,selenadiazole,phenanthridine ring were chosen for this propose.FIrstly,the evaluation of?S?-/?R?-11,11'-diethyl-11H,11'H-4,4'-dibenzo[a]carbazole-3,3'-diols is presented.?S?-/?R?-2,2'-Dihydroxy-7,7',8,8'-tetrahydro-[1,1'-binaphthyl]-5,5'-?6H,6'H?-dione,a key intermediate,is obtained by oxidation of?S?-/?R?-H₈-BINOL with DDQ in 1,4-dioxane and water,followed by reaction with CH₃I to protect hydroxyl groups.Then Fisher indole syntheses were performed with arylhydrazine hydrochlorides to afford indole-fused compounds,and N-substitutions is finished by the reacting with C₂H₅Br in the presence of base,followed by dehydrogenation with DDQ to give?S?-/?R?-11,11'-diethyl-3,3'-dimethoxy-11H,11'H-4,4'-bibenzo[a]carbazoles.Demethylation with BBr₃ were finalized to give?S?-/?R?-11,11'-diethyl-11H,11'H-4,4'-dibenzo[a]carbazo-le-3,3'-diols.The second part is focused on syntheses of diazole-fused binaphthols,?S?-/?R?-6,6'-dinanaphtho[1,2-c][1,2,5]oxadiazole/thiadiazole/selenadiazole-7,7'-Diphenols.The nitration of?S?-/?R?-BINOL with fuming HNO₃ led to 6,6'-dinitro-binaphthol,which reacted with CH₃I to form ether,then two amino groups at 5,5'-positions were introduced with ^tBuOK and 4-amino-1,2,4-triazole as amino source to form the key intermediates?S?-/?R?-2,2'-dimethoxy-6,6'-dinitro[1,1'-binaphthalene]-5,5'-diamine.The oxadiazoles?S?-/?R?-6,6'-dinanaphtho[1,2-c][1,2,5]oxadiazole-7,7'-diols could be obtained by the reaction of this key intermediate with NaClO in EtOH-NaOH to give the nitrogen oxides of oxadiazoles,which deoxidized with NH₂OH.HCl/KOH and finally demethylated with BBr₃.Asforthiadiazolesandselenadiazoles,?S?-/?R?-2,2'-dimethoxy-6,6'-dinitro-[1,1'-binaphthalene]-5,5'-diamine was reduced with SnCl₂/conc.HCl to form?S?-/?R?-2,2'-dimethoxy-[1,1'-binaphthalene]-5,5',6,6'-tetraamine hydrochlorides,which was treated by reaction with SOCl₂ or SeO₂ respectively to form thiadiazoles or selenadiazoles.The demethylations with aq.HBr or AlCl₃ give?S?-/?R?-6,6'-dinaphtho[1,2-c]-[1,2,5]thiadiazole-7,7'-diol/?S?-/?R?-6,6'-dinaphtho-[1,2-c][1,2,5]selenadiazole-7,7'-diol.The third part is to evaluate?S?-/?R?-[9,9'-dibenzo[a]phenanthridine]-10,10'-diols.6,6'-Dinitro-1,1'-binapthano-2,2'-diol,obtained by the nitration of?S?-/?R?-BINOL fuming HNO₃,reacted with CH₃I to form dimethoxy ethers,which were subsequently reduced with Pd/C-NH₂NH₂.H₂O to give?S?-/?R?-2,2'-dimethoxy-[1,1'-binaphthyl]-6,6'-diamines.Theminations with NBS form?S?-/?R?-2,2'-dimethoxy-5,5'-dibromo-[1,1'-binaphthyl]-6,6'-diamines,which reacted with phenylboronic acid by palladium-catalyzed Suzuki coupling,then acylated with acyl chloride,followed by the ring closure with P₂O₅/POCl₃.Then BBr₃ is employed for demethylation to give the target molecules?S?-/?R?-[9,9'-dibenzo-[a]phenanthridine]-10,10'-diols.