Solid-StateAlder-Ene Reaction of 1‑Hexeneunder High Pressure

The Alder-ene reaction is a chemical reaction between an alkene with an allylic hydrogen, and it provides an efficient method to construct the C–C bond. Traditionally, this reaction requires catalysts, high temperatures, or photocatalysis. In this study, we reported a high-pressure-induced solid-state Alder-ene reaction of 1-hexene at room temperature without a catalyst. 1-Hexene crystallizes at 4.3 GPa and polymerizes at 18 GPa, forming olefins. By exploring gas chromatography–mass spectrometry, we discovered that 1-hexene generates dimeric products through the Alder-ene reaction under high pressures. The <i>in situ</i> neutron diffraction shows that the reaction process did not obey the topochemical rule. A six-membered ring transition state including one C–H σ bond and two alkene π bonds was evidenced by the theoretical calculation, whose energy obviously decreased when compressed to 20 GPa. Our work offers a novel and promising method to realize the Alder-ene reaction at room temperature without a catalyst, expanding the application of this important reaction.