Total synthesis and determination of the absolute configuration of (−)-longilene peroxide

The first asymmetric total synthesis of (−)-longilene peroxide (1) has been achieved starting from the optically active C2-symmetric diepoxide 5 through the concept of two-directional synthesis utilizing its intrinsic molecular symmetry. Thus, the unknown absolute configuration of longilene peroxide has been determined by this synthesis as shown in the structural formula 1.