Molecular Transformation Based on Design of Novel Reaction Environment

目前的合作研究由以下四个小组进行：(1)基于新型单分子环境设计的分子转化；(2)基于新型多分子环境设计的分子转化；(3)基于新型生物模型系统设计的分子转化；(4)对新型分子环境设计的理论思考。第1组研究α -氧酰胺的反应。液晶或晶体中的乙炔、环己酮、对流层硫酮，并揭示了液晶或晶体等有序系统中可能存在的独特反应。第2组研究卟啉衍生物的多点相互作用，光合作用和视觉系统模型，以及环氧化作为加氧酶模型。第3组研究了羰基或活性氧在低温基质中的反应，独特的电解三氟甲基化，超大体积取代基作为独特分子环境的设计，以及BINAP-RU配合物的手性催化剂。这些结果表明，设计良好的单分子系统可以提供独特的分子环境。第4组研究了x射线晶体学分析系统的改进，从而使晶体相反应的晶体学数据能够非常准确地测量。对Si_<60>、Si_<24>、Si_<60>、H_<60>等硅簇进行了理论研究，揭示了硅簇与碳簇之间的有趣差异。

The present co-operative research has been carried out by the following four groups : (1)molecular transformation based on the design of novel monomolecular environment, (2)molecular transformation based on the design of novel multimolecular environment, (3)molecular transformation based on the design of novel biological model system, and(4)theoretical consideration of the design of novel molecular environment. Group 1 studied the reactions of alpha-oxoamides, . acetylenes, cyclohexenone, tropothione in liquid crystals or crystals, and revealed the possible unique reactions in ordered systems like liquid crystals or crystals. Group 2 studied multipoint interaction in porphyrin derivatives, photosynthesis and visual system model, and epoxidation as an oxygenase model. Group 3 studied the reactions of carbenes or active oxygen species in cryogenic matrices, unique trifluoromethylation by electrolysis, the design of extremely bulky substituent as a unique molecular environment, and, chiral catalyst by BINAP-RU complexes. These results suggest that well-designed monomolecular systems can provide unique molecular environment. Group 4 studied the improvement of X-ray crystallographic analysis system, thus enabling very fact measurement of cystallographic data for crystalline phase reactions. Theoretical studies on some silicon clusters like Si_<60>, Si_<24>, Si_<6O>H_<60> were carried out to reveal interesting differences between the silicon and carbon clusters.