Protonation of acenaphthoquinone. A novel peripheral 10 π-electron aromatic system

Acenaphthoquinone ($\text{1}$) undergoes ppotonation to afford the respective double protonation product $\text{2}$. The proton and carbon NMR parameters of $\text{2}$ are discussed.     

Anionic cyclization of a cross-conjugated enediyne

Cross-conjugated enediynes cannot follow the Bergman cycloaromatization as it involves a methylenediyne moiety with only five pi e(-), insufficient for aromatization. Under reductive conditions the cyclization is made feasible by generating a product with a Hückel number of pi electrons. We illustrate this principle and demonstrate for the first time an anionic cyclization of a cross-conjugated enediyne that results in formation of a five-membered ring. 9-(3-Phenyl-1-phenylethynylprop-2-ynylidene)-9H-fluorene (3) was reduced by potassium to yield the dianion of 9-(3,4-diphenylcyclopenta-2,4-dienylidene)-9H-fluorene (4(2-)), which contains a cyclopentadienyl fragment, and oxidation with iodine yielded the unstable fulvalene 4.     

Stereodynamics and characterization of the hexa(4-n-dodecylbiphenylyl)benzene hexaanion that includes a twisted benzene core

Hexa(4-n-dodecylbiphenylyl)benzene (HDBB) was reduced by a series of alkali metals in THF under high vacuum. Three reduction states were identified by NMR spectroscopy, namely the dianion, tetraanion and hexaanion. The NMR spectra of HDBB(6-) revealed a remarkable distortion of symmetry, which is interpreted by adoption of a twisted conformation of the central benzene ring and a slow rotation of the inner phenylene rings of the biphenyl units. Due to the surprising thermal stability of the hexaanion, a dynamic NMR investigation revealed the pseudorotation of the twisted conformation and the phenylene rotation mentioned above.     

Reduction of strained polycycles: how much strain can a pyrene anion take?

The reduction of a series of [n](2,7)pyrenophanes (n = 7-10) with lithium or potassium metal shows that the strain in the system, controlled by the length of the tether, determines the nature of the reduction products. The reduction of [7](2,7)pyrenophane (2) and [2]metacyclo[2](2,7)pyrenophane (3) leads to reductive dimerization followed by novel intramolecular sigma-bond formation as a means of escaping strained anti-aromaticity. [8](2,7)Pyrenophane (4) affords only reductive dimerization, and no two-electron reduction is observed. The reduction of [9](2,7) pyrenophane (5) and [10](2,7)pyrenophane (6) leads to reductive dimerization, followed by the formation of a dianionic anti-aromatic species, which eventually cleaves the solvent, THF-d(8). The similarity between the reduction of the latter systems and the reduction of pyrene (1) is discussed.     

"The great escape" from antiaromaticity: reduction of strained pyrenes

The two-electron reduction of strained pyrenes ([7](2,7)pyrenophanes) with lithium metal leads to the formation of a new sigma-bond as a means to "escape" strained antiaromaticity.