Impact of high-lying .sigma. orbitals and extensive through-bond interaction on chemical reactivity. 3. Solvolysis of syn- and anti-tricyclo[4.2.0.02,5]octa-3,5-diene derivatives

Abstract

Impact of High-Lying Orbitals and Extensive Through-Bond Interaction on Chemical Reactivity. 3. Solvolysis of syn-and antj-Tricyclo[4.2.0.02'5]octa-3,5-diene Derivatives1

Orbital interactions. 6. The Birch reduction as a tool for exploring orbital interactions through bonds. Through-three-bond interactions

“…Application of the commonly accepted31•37•39 mechanism of the Birch reduction to the reduction of a substrate 27 containing a double bond, D, whose orbitals interact with those of an aromatic ring, A, is shown in Scheme I. Addition of an electron to 27 generates a single radical anion 28 in which, by virtue of the presence of orbital interactions, the unpaired electron density is distributed over both D and A. Irreversible protonation53 of 28 may occur either at D or A to give the respective radicals 29 or 32. These species react further to give eventually 31 (reduction of D) and 34 (reduction of A).…”