6,6'-取代1,1'-联二萘酚衍生的手性磷酸的合成

Synthesis of Chiral Phosphoric Acids Derivated from 6,6'-Disubsituted BINOL

1,1'-联二萘酚(1)经溴代反应制得6,6'-二溴-1,1'-联二萘酚(2);2经苄基保护羟基制得2,2'-二苄氧基-6,6'-二溴-1,1'-联二萘(3);3经Ullmann缩合在6,6'-位引入甲氧基制得2,2'-二苄氧基-6,6'-二甲氧基-1,1'-联二萘(4b);3经Kumada偶联反应在6,6'-位引入正己基制得2,2'-二苄氧基-6,6'-二正己基-1,1'-联二萘(4c);4b和4c经还原脱去苄基制得6,6'-位取代1,1'-联二萘酚(5b和5c);2,5b和5c分别与三氯氧磷反应合成了3种1的6,6'-位取代手性磷酸(6a^6c),其结构经1H NMR和31P NMR表征。其中6c为新化合物。

The methoxyl group or hexyl group were successfully introduced to 6,6＇-position of the BINOL scaffold to get 2,2＇-bis（ benzyloxy）-6,6＇-dimethoxy-1,1＇-binaphthalene（ 4b） and 2,2＇-bis（ benzyloxy）-6,6＇-dihexyl-1,1＇-binaphthalene（ 4c） through Ullmann condensation and Kumada coupling,respectively.（ 6,6＇-Dibromo-1,1＇-binaphthyl-2,2＇-yl）-phosphoric acids（ 6a） was efficiently obtained by a two-step reaction from BINOL.（ 6,6＇-Dimethoxy-1,1＇-binaphthyl-2,2＇-yl）-phosphoric acid（ 6b） and（ 6,6＇-dihexyl-1,1＇-binaphthyl-2,2＇-yl）-phosphoric acid（ 6c） were synthesized by deprotection of 4b or 4c then condensation with phosphoryl trichloride. The structures were characterized by1H NMR and31P NMR. 6c was a new compound.