The total synthesis of biologically active, naturally occurring substances is an ambitious task. Fascinating new methods have been developed for the synthesis of natural products. We discuss the following accomplishments: (1) The short and convergent synthesis of 4,1-Bisdeoxydaunamycinone by Claisen/Diels-Alder sequence. (2) The regiochemical studies on the Diels-Alder reaction of electron-rich dienes and activated dienophiles, and the effort toward the aza-tricyclic moiety of atisine-type alkaloids. (3) The formation of bicyclic and monocyclic intermediates via silyl radical induced cyclizations, and the first chemoselective studies on silicon radicals.