Saito Hideaki, Mori Tadashi, Wada Takehiko, Inoue Yoshihisa
Department of Molecular Chemistry, Osaka University, 2-1 Yamada-oka, Suita 565-0871, Japan.
J Am Chem Soc. 2004 Feb 18;126(6):1900-6. doi: 10.1021/ja0370140.
The selective excitation of the charge-transfer (CT) complex and the direct excitation of the substrate gave distinctly different product ratios and diastereomeric excesses (de's), as well as their temperature dependencies, in [2 + 2] photocycloaddition of (E)-stilbene to bis((R)-1-methylpropyl) fumarate, clearly demonstrating that the excited CT complex and the conventional exciplex differ in structure and reactivity. This conclusion is supported by the contrasting fluorescence behavior exhibited by the relevant excited species, particularly at low temperatures.
在（E）-二苯乙烯与富马酸双（（R）-1-甲基丙基）酯的[2 + 2]光环加成反应中，电荷转移（CT）络合物的选择性激发和底物的直接激发产生了明显不同的产物比例和非对映体过量（de值），以及它们对温度的依赖性，清楚地表明激发的CT络合物和传统的激基复合物在结构和反应性上存在差异。这一结论得到了相关激发态物种所表现出的对比荧光行为的支持，尤其是在低温下。
