Kinetic Control in Natural Product Synthesis

Abstract The proper use of kinetic and thermodynamic control conditions in each reaction is indispensable to achieve total synthesis of complex natural product efficiently. Therefore, the reaction design based on kinetic control is always performed in the field of total synthesis. In this chapter, several examples of the effective use of kinetic and thermodynamic controls in the total synthesis of palau'amine are introduced. Our total synthesis of palau'amine is characterized by a Hg(OTf) 2 -catalyzed construction of the tetrasubstituted carbon center at the C16 position under thermodynamic control condition and the construction of the ABDE tetracyclic ring core including a trans -bicylo[3.3.0]octane skeleton under the kinetic control condition. The present synthetic route has the potential to help elucidate the pharmacophore of this natural product, as well as the mechanistic details of its immunosuppressive activity.