685076-78-2Relevant academic research and scientific papers
Photochemistry of 9-methylbicyclo[3.3.1]nonyl aryl ketones - A novel 1,5-disproportionation of 1,4-hydroxy biradicals and asymmetric induction using the solid-state ionic chiral auxiliary method
Chen, Shuang,Patrick, Brian O.,Scheffer, John R.
, p. 1460 - 1472 (2007/10/03)
A novel 1,5-disproportionation reaction has been discovered for 1,4-hydroxy biradicals derived from the photolysis of 9-methylbicyclo[3.3.1]nonyl phenyl ketones (1), which undergo mainly Yang cyclization both in solution and the solid state. By applying t
1,4-Hydroxybiradical Behavior Revealed through Crystal Structure-Solid-State Reactivity Correlations
Braga, Dario,Chen, Shuang,Filson, Heather,Maini, Lucia,Netherton, Matthew R.,Patrick, Brian O.,Scheffer, John R.,Scott, Carl,Xia, Wujiong
, p. 3511 - 3520 (2007/10/03)
Structure-reactivity correlations for triplet 1,4-hydroxybiradicals in solution are made difficult by the presence of multiple reactive conformers and the possibility of conformation-dependent intersystem crossing. These problems can be overcome by working in the crystalline state, where the conformations of the 1,4-hydroxybiradicals are fixed and determinable by X-ray crystallography of the parent ketones, assuming that hydrogen atom abstraction occurs with little or no change in conformation. This approach is applied to 15 bi- and tricyclic ketones designed to have slightly different biradical conformations, so that the effect of small and incremental changes in geometry on biradical behavior can be tested. The results indicate that, while geometry does have a strong influence on 1,4-hydroxybiradical partitioning between cyclization, cleavage, and reverse hydrogen transfer, a full understanding of the results requires that the strain involved in forming the cyclization products be taken into account.
