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

1.在5-位上带有被萘-1-基、萘-2-基、蒽-9-基或咔唑-9-基取代的3-羟基苯基的双环二氧杂环丁烷的合成及其碱诱导的化学发光分解：这些二氧杂环丁烷的合成通过相应的带有芳基的二氢呋喃的单重态氧化有效地实现。当这些二氧杂环丁烷单独处理t-BuOK络合物与各种冠醚在苯中，它们迅速分解为相应的酮酯与伴随的光发射，其颜色取决于冠醚用作t-BuOK络合物的配体。例如，对于带有3-羟基-2-氧杂环丁烷的分解，发射的颜色从橙子变为深红色。（9-蒽基）-5-羟基苯基部分。2.分子识别中的化学发光：碱诱导的带有双萘酚部分的光学活性二氧杂环丁烷与光学活性冠醚-叔丁醇钾络合物的分解：所合成的二氧杂环丁烷是具有取代联萘结构的立体异构双环二氧杂环丁烷，其C_1-C_1 '>键的轴向手性和环上碳的手性产生四种光学异构体，即（Ra，1R，5R）、（Ra，1S，5S）、（Sa，1S，5S）和（Sa，1R，5R）。当这些立体异构的二氧杂环丁烷分别用TBAF在DMSO中处理时，它们迅速分解为相应的酮酯，并伴随着闪烁红光的发射。当二氧杂环丁烷（Ra，1 R，5 R）与旋光冠醚的t-BuOK配合物反应时，在λ_（max）=615 nm处观察到化学发光<max><CL>。其他立体异构体与光学活性t-BuOK-复合物的类似处理也得到化学发光，其性质彼此不同。特别是，应该注意的是，1的四种立体异构体中的每一种都表现出不同形状的荧光光谱以及不同的最大波长。

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.