Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 125, Issue 18, Pages 5422-5430Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja028631b
Keywords
-
Categories
Ask authors/readers for more resources
We recently described a new photochemical rearrangement which we termed a Type C process. The reaction involves a 6 to a aryl migration in 5-disubstituted cyclohexenones also having bulky C-3 substituents. In contrast to most cyclohexenone rearrangements, the reaction occurs via a twisted pi-pi excited triplet rather than the usual n-pi* state. The electronic nature of the rearrangement was assessed using migration selectivity with p-anisyl and p-cyanophenyl groups. A synthesis of the reactants was elaborated, and the product structures were established by X-ray and NMR analysis. The reaction mechanism was established further with DFT and CASSCF computations. In the latter, localized NBO basis orbitals permitted proper selection of the active space. The nature of the diradical intermediates as well as the transition states was established computationally. Sensitization experiments with regioselectivities the same as those in direct irradiation confirmed the triplet multiplicity of the process.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available