Development and application of novel bond formation reactions of heteroaromatic compounds via iodonium intermediates.

联芳基化合物是合成天然产物、药物、农用化学品和π偶联有机材料的通用构件。因此，发展方便的交叉偶联反应得到联芳基是有机化学的重要课题之一。我发展了杂环化合物与二芳基碘盐的联芳基交叉偶联反应，得到了多种杂二芳基化合物。此外，我们还利用高价碘(III)试剂建立了无金属区域选择性氧化合成头尾(H-T)二硫吩类化合物的方法。这种独特的不对称偶联反应是通过3-取代噻吩类化合物的开关活性的碘中间体和中性3-取代噻吩类化合物在2-位的独占亲核性来实现的。

Biaryl compounds are versatile building blocks in the synthesis of natural products, pharmaceuticals, agricultural chemicals and π-conjugated organic materials. Therefore, the development of convenient cross-coupling reaction for giving biaryls is one of the important subjects in organic chemistry.I have developed the biaryl cross-coupling reaction of heteroaromatic compounds via diaryl iodonium salts, leading to various heterobiaryls. In addition, we also developed a metal-free regioselective oxidative synthesis of head-to-tail (H-T) bithiophenes using hypervalent iodine (III) reagent. This unique unsymmetrical coupling reaction was realized through the iodonium intermediate for the switching reactivity of 3-substituted thiophenes, and exclusive nucleophilicity of the neutral 3-substituted thiophenes at the 2-position.