The diastereoselective synthesis of organic molecules is an important research field and numerous important synthetic contributions have been made in recent years. 1 It was known that organoboranes derived from disubstituted olefins by hydroboration undergo a thermal isomerization at elevated temperatures (100–160°C). 2. and 3. We have shown that cyclic 3. and 4. and acyclic 5 tetrasubstituted olefins undergo a 1,2-thermal migration under milder conditions. Furthermore, these ...