C–H键活化反应在有机电子砌块合成及修饰中的应用

During the past several decades, C–H activation has received a great deal of attention as an effective approach for creating carbon-carbon and carbon-heteroatom bonds. C–H activation reactions can drastically shorten possible routes to a given chemicals by providing unprecedented disconnections in both the early and late stages. Herein, the project focused on the development of the novel strategies for selective C–H bond activation and sequential C–H bond activation of different C–H bonds and C–H bond activation-triggered cyclization/tandem reaction, which aimed at the efficient synthesis and precise modification of π-conjugated fragments, which play an important role in organic electronics. Our research also provides an opportunity to approach novel π-conjugated fragments, which might be difficult or impossible to build by traditional methods. From the point of view of synthetic organic chemistry, our study will promote the innovation and the further development of the field of C-H bond activation. From the perspective of material synthesis, the new C-H bond activation reactions will provide synthetic footstones for further development of organic electronics and simplifying the synthesis of the commercial available organic photoelectric materials. Based on this, the implementation of the project is expected to be fruitful, impressive and highly-impacted.

近年来，发展基于简单、廉价、与安全的反应原料中存在的C–H键的断裂与重组成键方法受到广泛关注，并取得长足进步。本项目着力于开发系列C–H键的定点活化及顺次活化策略，发展基于C–H键活化的成环/串联反应，旨在实现光电功能材料中具有重要作用的共轭砌块分子的高效合成及精确修饰。该方向上的研究将为构建传统方法难以或者无法达到的新型π-共轭砌块以及有机光电材料分子构效关系研究等提供机会。从合成方法学的角度出发，我们的研究将推动C–H键活化领域的革新和发展。从材料合成角度，新型C–H键活化反应的出现将为有机电子学的进一步发展提供合成基础，简化目前商业化应用的有机光电材料的合成，降低生产成本，推动有机电子学的商业应用。基于此，该项目的实施有望获得具有学科影响力的研究成果。

近年来，发展基于过渡金属催化环化反应以及后期官能化反应受到广泛关注，并取得长足进步。本项目负责人着力于利用过渡金属催化，构筑系列在有机光电材料方向上具有重要应用前景的π-共轭体系。通过本项目的实施，分别发展了基于铑催化的分子内的C–H键硅基化反应，实现了Si-O桥联的π-共轭体系及梯形分子的高效构筑，并系统阐述了“取代基效应”、“异构体效应”及“硅效应”在对该类分子光物理性质的影响。同时他们还分别发展了具有共轭特征的（苯并）硅杂环庚烯酮的高效化学合成；3-位取代的噻吩并[3,4-b]-噻吩骨架的高效化学合成；零价镍催化的转移氢化参与的氧化型HECK反应等。这些研究成果包括所合成的新型共轭骨架以及所发展的新型过渡金属催化的反应有望推动有机电子学方向上新材料的发现这一重要领域。项目执行期内，项目负责人发表了与该项目相关的高水平研究论文9篇。基中包括Angew. Chem. Int. Ed 1 篇；Nat. Commun.1篇；ACS Catal. 2篇；Chem. Sci. 2篇。