Hyperpyramidalized alkenes with bond orders near 1.5 as synthetic building blocks

Abstract Alkenes typically have trigonal planar geometries at each terminus, with favourable σ- and π-bonding leading to a bond order of ~2. Here we consider unusual alkenes that possess an extreme form of geometric distortion, termed hyperpyramidalization. In a hyperpyramidalized alkene, geometries deviate remarkably from the typical trigonal planar alkene geometry, leading to weak π-bonding and abnormal alkene bond orders approaching 1.5. Cubene and 1,7-quadricyclene, first validated in 1988 and 1979, respectively, but overlooked for decades since, are the focus of the present study. We leverage their unusually weak π-bonds in cycloadditions, enabling the construction of complex scaffolds and access to previously unrealized chemical space. The origins of the unusually low bond orders were investigated using computational methods. These efforts are expected to prompt future studies of molecules that display hyperpyramidalization or atypical bond orders.