生体透過性近赤外光で活性化される抗シュヨウ性分子の合成と機能

概要

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One-way geometrical isomerization around a C=C bond of 1,1-diaryl-2-t-butylethene isachieved upon photoirradiation of cyanoaromatics as a light-absorbing sensitizer. In thethermochemical view, there is no difference between both E and Z isomers of the ethene. In view ofthe structural resemblance of the ethene to some commercially available antitumor pharmaceuticals,the reaction seems to be of interest to examine extensively. Tuning of wavelength of the light wouldbe possible because the reaction is basically a photocatalytic reaction. Key intermediate is a putativedistonic cation radical of which is a unique one having a spatially separated radical and ionic centerson the molecular framework. Generation of such an intermediate is due to the presence of ap-electron donating substituent on an aromatic ring and a bulky t-butyl group. Molecular oxygeninteracts as superoxide with the C=C bond of the cation radical in a [supra + antara] manner to give adecomposition product, i.e. a benzophenone derivative and pivalaldehyde, via a dioxetane andcompetitively, one geometrical isomer of the ethene is afforded by splitting oxygen before makingtwo bonds with the ethene cation radical and superoxide.
徳島大学の論文