ABSTRACT
Synthesis of dehydoriso-ß-lapachone (1) in both racemic and enantioenriched forms is achieved starting from reduced naphthoquinone equivalents. As for the synthesis of enantioenriched dehydroiso-ß-lapachone, introduction of the asymmetric center was carried out by catalytic asymmetric epoxidation of the unfunctionalized trisubstituted olefin using Shi epoxidation diketal catalyst. The construction of isopropenylfurano-1,2-(ß)-naphthoquinone was carried out by acidic ring-opening reaction of the epoxynaphthalene and the following diammonium cerium(IV) nitrate (CAN) oxidation. The absolute configuration of naturally occurring (-)-dehydroiso-ß-lapachone was finally determined as (R) by comparing the measured optical rotation value of the synthetic (R)-dehydroiso-ß-lapachone.
