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Generation of Stable Biradical Intermediates in Intramolecular Photo-Cycloaddition of Aromatic Compounds

芳香族化合物分子内光环加成生成稳定的双自由基中间体

基本信息

批准号：
07640710
负责人：
YAMADA Kazutoshi
金额：
$ 0.45万
依托单位：
CHIBA University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

In order to establish the highly stereo and peri-selective in an aromatic photo-cycloaddition and to elucidate the involvementof biradical intermediates, photochemical reactin of N-naphthamides and N-cimmamides were examined.,(1) Inter- and Intra- molecular selection of photo-cycloaddition ; In the photo-cycloadditin of N-cimmanoylnaphthamides, the intramolecular cycloaddion occurred in solution and the intermolecular cycloadition was achieved in the solid state reaction depending on the substituents.(2) The control of the peri-selectivity ; This was achieved in the photo-cycloaddition of N-1- (1-naphthyl) ethyl-cimmamides and N-1- (1-naphthyl) ethylacryl amides. In the former, the intramoleclar [4+2] cycloaddition was achieved and the [2+2] cycloaddition was achieved in the latter.(3) Novel [2+2] photo-cycloaddition of a benzene ring with an enone double bond ; This rare example of the [2+2] photo-cycloaddition was observed in N-benzoylcimmamides.(4) Generation of a biradical intermediate and its trapping with molecular oxygen ; The 1,8 biradical intermediate was generated in the intramolecular photo-cycloaddition of N-naphthoylnaphtamides. The generated biradical intermediate was efficiently trapped with molecular oxygen. The life time of the intermedaite was determined by laser flash photolysis.(5) Asymmetric photo [4+4] cycloaddition ; The first example of an absolute asymmetric synthesis in aromatic photo-cycloaddion was achieved in the solid-state photochemistry of N-anthronylnaphthamieds.

为了建立芳香族光环加成反应中的高立体选择性和高周位选择性以及阐明双自由基中间体的参与，研究了N-萘酰胺和N-亚胺酰胺的光化学反应。(1)光环加成反应的分子间和分子内选择性在N-辛酰萘酰胺的光环加成反应中，根据取代基的不同，分子内环加成反应在溶液中进行，分子间环加成反应在固相反应中进行。(2)这是在N-1-（1-萘基）乙基亚胺酰胺和N-1-（1-萘基）乙基丙烯酰胺的光环加成反应中实现的。前者实现了分子内的[4+2]环加成，后者实现了[2+2]环加成。(3)苯环与烯酮双键的[2+2]光环加成反应这是在N-苯甲酰亚胺中观察到的一个罕见的[2+2]光环加成反应。(4)一种双自由基中间体的产生及其与分子氧的捕获研究在N-萘甲酰基萘酰胺的分子内环加成反应中产生了1，8双自由基中间体。所产生的双自由基中间体被有效地捕获与分子氧。用激光闪光光解法测定了中间体的寿命。(5)不对称光[4+4]环加成反应：在N-蒽酮基萘酰胺的固态光化学反应中实现了芳香族光环加成反应中的第一个绝对不对称合成。