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

带有阻转异构联芳基部分的光学活性二氧杂环丁烷的设计与合成

基本信息

批准号：
14540506
负责人：
MATSUMOTO Masakatsu
金额：
$ 2.24万
依托单位：
Kanagawa University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2004
项目状态：
已结题

项目摘要

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.

1.含3-羟基苯基的双环二氧杂环烷的合成及其碱诱导化学发光分解：这些二氧杂环烷的合成是通过相应的含芳基的二氢呋喃单线态氧化的方法实现的。当这些二氧杂环己烷分别用t-BuOK与不同的冠醚在苯中络合时，它们会迅速分解成相应的酮酸酯，并伴随着发光，发光的颜色取决于作为t-BuOK络合物的配体的冠醚。2.分子识别中的化学发光：碱诱导的含有双萘酚结构的光学活性二氧杂环烷与光学活性冠醚-叔丁醇钾的络合物的分解：合成的二氧杂环烷是含取代联萘结构的立体异构体双环酮，其轴向手性围绕C_1-C_&lt；1‘&gt；二氧杂环碳的键和手性形成四个光学异构体，即(Ra，1R，5R)，(Ra，1S，5S)，(Sa，1S，5S)和(Sa，1R，5R)。当这些立体异构体二氧杂环己烷在DMSO中分别用四溴联苯并呋喃处理时，它们迅速分解成相应的酮酸酯，并伴随着闪烁的红光。当二氧杂环己烷(Ra，1R，5R)与光学活性冠醚的t-BuOK-络合物反应时，在λ_&lt；max&gt；^&lt；CL&gt；=615 nm处观察到化学发光。用光学活性的t-BuOK络合物对其他立体异构体进行类似的处理也得到了化学发光，但性质各不相同。特别值得注意的是，1的四个立体异构体中的每一个都显示出不同形状的化学发光光谱以及不同的最大波长。

项目成果

期刊论文数量（43）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

M.Matsumoto: "Synthesis of 5-tert-butyl-1-(3-tert-butyldimethylsiloxy)phenyl-4,4-dimethyl 2,6,7-trioxabicyclo[3.2.0]heputanes and their fluoride-induced-----"Luminescence. 17. 305-312 (2002)

M.Matsumoto：“5-叔丁基-1-(3-叔丁基二甲基硅氧基)苯基-4,4-二甲基2,6,7-三氧杂双环[3.2.0]庚烷的合成及其氟化物诱导——

DOI：
发表时间：
期刊：
影响因子：
0
作者：
通讯作者：

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.

DOI：
10.1039/b414001j
发表时间：
2005-02
期刊：
Chemical communications
影响因子：
4.9
作者：
M. Matsumoto;Koji Hamaoka;Yuji Takashima;Mizuki Yokokawa;Kazutaka Yamada;N. Watanabe;H. K. Ijuin
通讯作者：
M. Matsumoto;Koji Hamaoka;Yuji Takashima;Mizuki Yokokawa;Kazutaka Yamada;N. Watanabe;H. K. Ijuin

Chemiluminescent decomposition of a dioxetane bearing a 3-(1-cyanoethenyl)phenyl moiety induced by Michael addition of an anion of malonate

丙二酸阴离子迈克尔加成诱导带有 3-(1-氰基乙烯基)苯基部分的二氧杂环丁烷的化学发光分解