Study of Reactive Intermediates in Photoinduced Electron Transfer Anti-Markovnikov Addition of MEthanol to 1-Phenyclcoalkenes

Masanobu Kojima; Akito Ishida; Yasunao Kuriyama; Yuji Wada; Haruhiko Takeya

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Study of Reactive Intermediates in Photoinduced Electron Transfer Anti-Markovnikov Addition of MEthanol to 1-Phenyclcoalkenes

机译：甲醇对1-苯酚的光诱导电子转移反马尔科夫尼科夫加成反应中中间体的研究

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Irradiation of 1-phenylcycloalkenes (1) with cyanoaromatics as electron-accepting sensitizers in MeCN and PhH containing 1.0 M MeOH gave trans- (2) and cis-isomers (3) of anti-Markovnikov adducts. It was found that the isomer ratio of 2/3 depended on the size of 1 and solvent polarity, but not on the sensitizers used. The mechanisms for adduct formation in MeCN and PhH were studied by means of fluorescence spectroscopy, pulse radiolysis, and semiempirical molecular orbital calculation (PM) and are dissussed on the basis of the reactivities of the three kinds of intermediates involved in the reaction [cation radicals of 1 (1~(.+)), free radicals generated by addition of Me OH to 1~(.+), and carbanions produced by reduction of the free radicals by anion radicals of the sensitizersl]. On the asis of the results obtained by the calculation, it is concluded that the ratio of 2/3 in MeCN is dependent on the structures and stabilities of the radicals and carbanions, while for PhH the formation of exciplex between 1 and the sensitizers causes cis addition of MeOH to 1 due to steric hindrance, finally to yield 2 as the predominant adduct.

机译：在含有1.0 M MeOH的MeCN和PhH中，用氰基芳族化合物作为电子接受敏化剂辐照1-苯基环烯烃（1），得到反马氏复合物的反式（2）和顺式异构体（3）。发现2/3的异构体比率取决于1的大小和溶剂极性，而不取决于所使用的敏化剂。通过荧光光谱，脉冲辐射分解和半经验分子轨道计算（PM）研究了MeCN和PhH中加合物的形成机理，并根据参与反应的三种中间体[阳离子自由基]的反应性进行了讨论。 1（1〜（。+）），通过向1〜（。+）添加Me OH生成的自由基以及通过敏化剂的阴离子自由基将自由基还原而产生的碳负离子]。根据计算结果，可以得出结论，MeCN中2/3的比例取决于自由基和碳负离子的结构和稳定性，而对于PhH，在1和敏化剂之间形成激基复合物会导致顺式由于空间位阻，将MeOH加到1中，最后得到2作为主要加合物。

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《Bulletin of the Chemical Society of Japan》 |1999年第5期|共7页
作者
Masanobu Kojima; Akito Ishida; Yasunao Kuriyama; Yuji Wada; Haruhiko Takeya;
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中图分类化学;化学工业;
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机译：甲醇对1-苯酚的光诱导电子转移反马尔科夫尼科夫加成反应中中间体的研究
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Study of Reactive Intermediates in Photoinduced Electron Transfer Anti-Markovnikov Addition of MEthanol to 1-Phenyclcoalkenes

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