1449565-80-3Relevant academic research and scientific papers
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
Nakagaki, Tomoyuki,Sakai, Tomoko,Mizuta, Tsutomu,Fujiwara, Yoshihisa,Abe, Manabu
, p. 10395 - 10404 (2013/09/02)
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 (DRs). 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) 2H5) 3H7) ≈2292 ns (DRe; OR=OR′=OC 6H13) ≈2146 ns (DRf; OR=OR′=OC10H 21). 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. Copyright
