Kinetic Stabilization and Reactivity of π Single‐Bonded Species: Effect of the Alkoxy Group on the Lifetime of Singlet 2,2‐Dialkoxy‐1,3‐diphenyloctahydropentalene‐1,3‐diyls

Kinetic stabilization and reactivity of π single‐bonded species have been investigated in detail by generating a series of singlet 2,2‐dialkoxy‐1,3‐diphenyloctahydropentalene‐1,3‐diyls ( DR s). The lifetime at 293 K in benzene was found to increase when the carbon chain length of the alkoxy groups was increased; 292 ns ( DRb ; OR=OR′=OCH₃) <880 ns ( DRc ; OR=OR′=OC₂H₅) <1899 ns ( DRd ; OR=OR′=OC₃H₇) ≈2292 ns ( DRe ; OR=OR′=OC₆H₁₃) ≈2146 ns ( DRf ; OR=OR′=OC₁₀H₂₁). DRh (OR=OC₃H₇, OR′=OCH₃; 935 ns) with the mixed‐acetal moiety is a longer‐lived species than another diastereomer DRg (OR=OCH₃, OR′=OC₃H₇; 516 ns). Activation parameters determined for the first‐order decay process reveal that the enthalpy factor plays a crucial role in determining the energy barrier of the ring‐closing reaction, that is, from the π‐bonding to the σ‐bonding compounds. Computational studies using density functional theory provided more insight into the structures of the singlet species with π single‐bonded character and the transition states for the ring‐closing reaction, thereby clarifying the role of the alkoxy group on the lifetime and the stereoselectivity of the ring‐closing reaction.