Tetravinylethylene

The first four‐fold cross coupling reaction involving alkenic partners leads to the title hydrocarbon on multi‐gram scale in one step from commercially available precursors. In stark contrast to its close structural relatives, tetravinylethylene is a remarkably robust, bench‐stable compound. The π‐bond rich hydrocarbon is shown to undergo one‐pot sequences of pericyclic reactions leading to the formation of complex systems with four new rings, seven CC bonds and ten stereocenters with a very high level of stereoselectivity. Insights into the reactivity of this and related systems is provided using the accurate composite ab initio MO G4(MP2) method. Targets very efficiently: The forgotten hydrocarbon, tetravinylethylene (TVE, scheme) is a bench‐stable compound that can be synthesized in one step from commercially available starting materials. TVE is a vehicle for rapid complex molecule synthesis through one‐pot sequences involving the stereoselective assembly of up to seven CC bonds.