Design and Synthesis of Optically Active Dioxetanes Bearing an Atropisomeric Biaryl Moiety

点击翻译按钮获取中文摘要

1.Synthesis of bicyclic dioxetanes bearing a 3-hydroxyphenyl substituted with naphthalen-1-yl, naphthalen-2-yl, anthracen-9-yl, or carbazol-9-yl group at the 5-position and their base-induced chemiluminescent decomposition : Synthesis of these dioxetanes were effectively attained by means of singlet oxygenation of the corresponding dihydrofurans bearing an aryl group. When these dioxetanes were treated individually with t-BuOK complexed with various crown ethers in benzene, they decomposed rapidly to the corresponding keto esters with accompanying emission of light, which varied in color depending on the crown ether used as a ligand of t-BuOK complex. For example, the color of emission changed from orange to crimson for the decomposition of a dioxetane bearing a 3-(9-anthryl)-5-hydroxyphenyl moiety.2.Chemiluminescence in molecular recognition : base-induced decomposition of optically active dioxetanes bearing a bisnaphthol moiety with a complex of optically active crown ether-potassium tert-butoxide : Dioxetanes synthesized were stereoisomeric bicyclic one bearing a substituted binaphthyl moiety, for which axial chirality around C_1-C_<1'> bond and chirality of carbon in the dioxetane ring give rise to four optical isomers, namely (Ra,1R,5R), (Ra,1S,5S), (Sa,1S,5S), and (Sa,1R,5R). When these stereoisomeric dioxetanes were individually treated with TBAF in DMSO, they decomposed rapidly to the corresponding ketoesters with accompanying emission of flash red light. When a dioxetane (Ra,1R,5R) was treated with a t-BuOK-complex of an optically active crown ether, chemiluminescence was observed with λ_<max>^<CL>=615 nm. Similar treatment of the other stereoisomers with optically active t-BuOK-complex gave also chemiluminescence, properties of which were different from each other. Especially, it should be noted that each of the four stereoisomers of 1 exhibited different shapes of the chemiluminescent spectrum as well as different maximum wavelength.