75011-40-4Relevant academic research and scientific papers
Photochemistry in a crystalline cage. Control of the Type-B bicyclic reaction course: Mechanistic and exploratory organic photochemistry
Zimmerman,Sebek
, p. 3677 - 3690 (2007/10/03)
Our current theories on crystal lattice control of organic photochemistry were subjected to studies of type-B rearrangement of bicyclo[3.1.0]hex-3-en-2-ones. A first finding was that the solid state photochemistry differed dramatically from that in solution. One of our past observations in this bicyclic photochemistry in solution was that the six-membered ring, type B, zwitterion was a ubiquitous intermediate. This intermediate invariably underwent a preferential migration of an aryl group to carbon-2 relative to carbon-4 with formation of a 2,3-disubstituted phenol, a result deriving from electronic effects. In contrast, the crystal lattice photochemistry revealed a regioselectivity depending on the surrounding lattice rather than electronics. Perhaps an even more dramatic difference was an observation of the dependence of reactant stereochemistry. Thus, in solution, for 6,6-disubstituted bicyclics with two different groups at C-6, a common zwitterion is formed and the same photoproduct is formed independent of reactant stereochemistry. In crystal lattices the endo and exo stereoisomers of the 6,6-disubstituted bicyclics react differently and the group originally endo tends to migrate after three-ring opening to the zwitterion. The experimental results were paralleled with a theoretical analysis. This consisted of generation of a 'mini crystal lattice' with sufficient lattice molecules to completely surround a central, reacting electronically excited state molecule. Then computational extraction of the central molecule and replacement by a transition structure afford a model of the reacting excited state inside the crystal lattice. Overlap of this species with the lattice neighbors and energy computations are then possible. These permit prediction and understanding of excited state crystal lattice reactivity on a quantitative basis.
Regioselectivity in Cyclohexadienone Photochemistry. Role of Zwitterions in Type A Photochemical and Dark Rearrangements. Mechanistic and Exploratory Organic Photochemistry
Zimmerman, Howard E.,Pasteris, Robert J.
, p. 4864 - 4876 (2007/10/02)
The photochemistry of 3-cyano-4,4-diphenyl-2,5-cyclohexadienone was investigated to elucidate the regioselectivity of the type A rearrangement.Although, a priori, both 4-cyano-6,6-diphenylbicyclohex-3-en-2-one and 5-cyano-6,6-diphenylbicyclo
