Development of Hypervalent Iodine Compounds for New Medicines and Agricultural Chemicals

(1)邻三甲基硅基苯基碘鎓盐在温和条件下能有效地合成苄炔类化合物，并具有较高的生物活性。本研究为合成含不同羰基的苯炔类化合物提供了一种新的方法。苯炔前体有效地产生苯炔，而不损害反应性羰基。此外，本研究还涉及高价碘-苯炔前体的合成，其可溶于低极性溶剂如乙醚、苯和甲苯。有趣的是，此类前体甚至在己烷中也会发生反应。(2)杂环高价碘化合物的研究进展杂环高价碘化合物可用于生成杂苯炔，在合成和生物学上都是一个令人感兴趣的化合物。我们已经开发了具有异恶唑结构的高价碘化合物的合成。虽然三甲基甲硅烷基取代的异恶唑碘鎓盐预期生成脱氢异恶唑，但它们通过环连接反应得到亚硝酸盐衍生物。(3)高价碘低聚物的开发：我们发现碘苯二乙酸酯在三氟甲磺酸中反应生成高价碘低聚物。我们独立地制备了高价碘三聚体和四聚体，并证实了高价碘低聚物的结构，具有对亚苯基结构，本研究制备的高价碘化合物显示出生物活性。特别地，高价碘低聚物对出芽短梗霉和绳状青霉表现出体外毒性，并且对细菌物种表现出强毒性。

(1) Development of Hypervalent Iodine-Benzyne PrecursorsWe have found that o-(trimethylsilyl)phenyliodonium salts efficiently generate benzynes under very mild conditions and show a high biological activity. This study provides a new method for synthesis of benzyne precursors bearing various carbonyl groups. The benzyne precursors efficiently generate benzynes without damage of reactive carbonyl groups. Also, this study involves synthesis of hypervalent iodine-benzyne precursors soluble is a low polarity of solvents such as ether, benzene and toluene. Interestingly, such precursors react even in hexane.(2) Development of Heterocyclic Hypervalent Induce CompoundsHeterocyclic hypervalent iodine compounds applicable to generation of heterobenzynes are interesting synthetically and biologically. We have developed the synthesis of hypervalent iodine compounds having an isoxazole structure. Although the trimethylsilyl-substituted isoxazolyliodonium salts are expected to generate dehydroisoxazoles, they give nitrite derivatives by ring-opining reactions.(3) Development of Hypervalent Iodine Oligomers.We have found that reaction of iodobenzene diacetate in trifluoromethanesulfomic acid gives hypervalent iodine oligomers. Independently, we prepared hypervalent trimer and tetramer and confirmed the structure of hypervalent iodine oligomers, having a para-phenylene structure.The hypervalent iodine compounds prepared in this study show a biological activity. Particularly, hypervalent iodine oligomers exhibit a vitro toxicity against Aureobasidium pullulans and penicillium funiculosum and strong toxicity against bacterial species.