Development of Highly Efficient Oxidation Reaction and Polymerizaztionby Utilizing the Oxidizing Ability of HyPERvalent Bismuth

我们已经研究了三个主要课题，通过利用五价铋的特性开发新的反应（氧化和光诱导阳离子聚合）。首先，合成了各种四芳基铋盐，并将其用作醇氧化的氧化剂。在有机碱存在下，通过用上述Bi（V）氧化剂处理，伯醇和仲醇有效地转化为相应的羰基化合物。已经发现，在芳基配体上引入邻位取代基和/或吸电子对位取代基显著增强铋盐的氧化能力。特别地，均三甲苯基三芳基铋盐在伯醇和仲醇之间的竞争反应中表现出高氧化能力和高化学选择性。其次，我们首次开发了高效的Bi（V）基阳离子光引发剂。三芳基（1-芘基）铋盐在乙腈中的光辐射得到三芳基铋烷和芘，伴随着质子酸的产生。三芳基（1-芘基）铋鎓六氟锑酸盐已被证明是环氧乙烷和乙烯基醚的阳离子聚合的有效光引发剂，在短的光照射时间内以良好的产率提供相应的聚合物。在寻找有望光引发Bi介导的阳离子聚合的光敏剂的过程中，我们设计了一类在中位带有磷和硫取代基的新型卟啉。最后，我们成功地合成了几种meso-磷酰基卟啉和meso-亚磺酰基卟啉，并对其结构、光学性质和电化学性质进行了详细的研究。

We have investigated three main topics to develop new reactions (oxidations and photo-induced cationic polymerizations) by utilizing the characteristic properties of the pentavalent bismuth. Firstly, various tetraarylbismuthonium salts were prepared and used as oxidants for alcohol oxidation. Primary and secondary alcohols were efficiently converted to the corresponding carbonyl compounds by treatment with the above Bi(V) oxidants in the presence of an organic base. It has been found that the introduction of ortho-substituents and/or electron-withdrawing para-substituents onto the aryl ligands enhances the oxidizing ability of the bismuthonium salts significantly. In particular, mesityltriarylbismuthonium salts exhibit high oxidizing ability and high chemoselectivity in the competitive reactions between primary and secondary alcohols. Secondary, we developed highly efficient Bi(V)-based cationic photoinitiators for the first time. Photoirradiation of triaryl(1-pyrenyl)bismuthonium salts in acetonitrile afforded triarylbismuthanes and pyrene, accompanied by the generation of protic acids. Triaryl(1-pyrenyl)bismuthonium hexafluoroantimonates have proven to behave as efficient photoinitiators for the cationic polymerization of oxiranes and a vinyl ether, affording the corresponding polymers in good yields within a short photoirradiation time. During the search of sensitizers, which were anticipated to photoinitiate the Bi-mediated cationic polymerization, we designed new classes of porphyrins bearing phosphorus and sulfur substituents at the meso position. Finally, we successfully prepared several meso-phosphorylporphyrins and meso-sulfinylporphyrins, and elucidated their structures, optical properties, and electrochemical properties in detail.