| Asymmetric reductive cyclization; the total synthesis of (;TMM diyl atom transfer reaction; application toward the total synthesis of confertin. The TMM diyl atom transfer reaction provides an efficient means for the generation of (5.3.0) and (6.3.0) skeletons. This methodology has been applied to the total synthesis of the pseudoguaianolide confertin. The atom transfer reaction of diazene 119 provides the tricyclic material 122 in 48% yield while providing functionality needed to complete the synthesis. This synthetic scheme also highlights the use of an organometallic endoperoxide opening methodology and an improved electrochemical synthesis of diazenes.;The reductive electrochemistry of conjugated nitroalkenes. The use of conjugated nitroalkenes as substrates for electroreductive cyclization, electrohydrodimerization, and electrohydrocyclization reactions has been evaluated. In divided cells, the chemistry is dominated by acid/base chemistry affording dimers. However, in an undivided cell, the electrohydrodimer is formed in excellent yield. Using CV, UV and ESR data on the radical anion of 151, as well as calculations on four analogous olefins, a mechanism of the reductive behavior of nitroalkenes has been proposed. |
