Strategies for the Synthesis of Sulfur-containing Heteroacenes

化学科学家受到天然产物合成的启发，开发出高度复杂的有机转化方法。令人惊讶的是，这种发展有机材料有效合成方法的趋势很少被观察到。然而，有机材料合成的有效方法的发展是至关重要的。这种缺乏这样的合成方法是解决在目前的项目通过现代过渡金属催化高效合成含硫杂环烯。硫基发光杂苯化合物是一种半导体，在有机场效应晶体管（OFET）中有广泛的应用。进入这种结构往往受到使用剧毒和/或对湿气和氧敏感的硫试剂的限制。提出的项目保证了不同取代的聚苯乙烯硫和含硫/含氮杂苯醚的直接方法。这是通过C-S交叉偶联/环化多米诺反应实现的，使用硫脲作为简单安全的硫替代品。与此策略互补的是二芳基硫醚和二芳胺的分子内环化。双（噻吩）硫醚或双（噻吩）胺的分子内C-H活化/C-C偶联提供了获得双噻吩和双噻吩的途径。环化前体的模块化合成保证了高多样性，从而允许系统的电子特性的调制。新的杂化物将被评估其作为半导体在OFET器件中的功能。

Chemical scientists have been inspired by natural product synthesis to develop highly sophisticated methodologies for organic transformations. Surprisingly, such tendency to develop methodologies for the efficient synthesis of organic materials can only be sparingly observed. However, the development of efficient methodologies for the synthesis of organic materials is of utmost importance. This lack of such synthetic methodology is addressed in the presented project by the efficient synthesis of sulfur-containing heteroacenes by modern transition metal catalysis.Sulfur-based anellated heteroacenes are semi-conductors, which find application in organic field-effect-trasistors (OFET). The access to such structures is often limited by the use of highly toxic and/or moisture- and oxygen-sensitive sulfur reagents. The presented project warrants for the straightforward approach to diversely substituted polyanellated sulfur- and sulfur/nitrogen-containing heteroacenes. This is achieved by a C-S cross coupling/cyclization domino reaction using thiourea as easy and safe to handle sulfur surrogate. Complementary to this strategy is the intramolecular cyclization of diarylthioethers and diarylamines by C-H activation. The intramolecular C-H activation/C-C coupling of bis(thiopene)thioethers or bis(thiophene)amines provides access to bisthienothiophenes and bisthienopyrroles. The modular synthesis of the cyclization precursors warrants for high diversity, thus allowing the modulation of the electronic properties of the systems.Novel heteroacenes will be evaluated in their capabilities to function as semi-conductors in OFET devices.