Xianfu Shen, Yongyun Zhou, Yongkai Xi, Jingfeng Zhao, Hongbin Zhang
In this paper, we report a full account of the synthesis of dimeric hexahydropyrroloindole alkaloids and its analogues. The key feature of our new strategy is the novel catalytic copper (10%) mediated intramolecular arylations of o-haloanilides followed by intermolecular oxidative dimerization of the resulting oxindoles in one pot. This sequential reaction leads to the key intermediates for the synthesis of (+)-chimonanthine, (+)-folicanthine, (-)-calycanthine and (-)-ditryptophenaline. Graphical Abstract In the presence of catalytic amount of cuprous iodide (10%), an intramolecular arylation of ohaloanilidesfollowedby an intermolecularoxidative dimerizationof the resultingoxindolesleads to a commonintermediatefor the synthesis of (+)-chimonanthine, (+)-folicanthine and (-)-calycanthine. Based on this cascade sequence, we also developed a flexible strategy towards the asymmetric syntheses of dimeric HPI alkaloids (-)-ditryptophenaline and its analogues.