Recently, the research team led by Jingjing Wu at the Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, has achieved significant research progress. The related findings have been published in CCS Chem under the title: " Bioinspired Schenck-ene/Hock/aldol cascade reaction Enables Concise Synthesis of Natural Products Alstoscholarinoid A, Masterpenoid D, Leontogenin and Marsformoxide B.".

Article abstract:

In this paper, we achieved the concise synthesis of four natural products-alstoscholarinoid A, masterpenoid D, leontogenin, and marsformoxide B-through a skeletal editing strategy. Our approach featured a novel bioinspired Schenck-ene/Hock/aldol cascade reaction to generate the core skeletons of target molecules. This reaction rapidly constructs the complex terpenoid skeletons from alkene or diene substrates with excellent functional group compatibility, enabling the synthesis of alstoscholarinoid A (on hundred-milligram scale), masterpenoid D, and leontogenin. Besides the expected σ-bond migration, we also observed the migration of π-bond during the Hock rearrangement of the hydroperoxide intermediate, which enabled the biomimetic synthesis of another natural product marsformoxide B. Computational studies further unveiled the factors dominating the different rearrangement pathways of hydroperoxide. Overall, these studies have demonstrated the Schenck-ene/Hock/aldol cascade reaction as an inspiring strategy for the synthesis and skeletal editing of natural products.