基于Atrane结构锗硼试剂的烯烃和炔烃官能化

Suzuki reaction, as well as Hiyama/Stille reaction always complement each other, enrich the cross-coupling chemistry. The functionalization of alkynes/alkynes with Si-B/Ge-B/Sn-B reagents is an effective way to introduce both boron and group 14 elements simultaneously, whereas there is only one such commercial available reagent: DMPS-Bpin, and DMPS (Dimethylphenylsilyl) is not an effective coupling fragment in organic system..The toxicity of germanium is lower than that of tin while the coupling reaction activity is higher than that of silicon. Germatrane leads to higher reaction activity than the open-chain germanium reagent through the intramolecular coordination of nitrogen atoms. Accordingly, this project intends to develop Germatrane-Boron reagents for the functionalization of alkynes/alkynes. The resulting Germatrane-containing block is a novel coupling fragments with highly efficiency. While most functionalization study of alkynes/alkynes focus on the catalyst, less attention is paid to the perspective of new reagents. China has 41% of the world's reserves of germanium, exploration of Germatrane has been patented. Applicants has several publications in JACS, Angew and Nat. Commun, which show good foundation for the study.

Suzuki反应和14族元素的Hiyama、Stille反应往往性能互补，共同丰富了有机交叉偶联化学。硅锗锡的硼化物对烯、炔的官能化是同时引入硼和14族元素的有效途径，然而商业化的这类试剂只有一种：二甲基苯基硅-频哪醇硼酯，且二甲基苯基硅在引入有机体系后并非一种有效的偶联片段。.锗的毒性低于锡且偶联反应活性高于硅。Atrane结构的笼状锗更是通过分子内氮原子的跨环配位导致超越开链锗试剂的反应活性。据此，本项目拟发展笼状锗硼试剂用于烯炔功能化反应，所得含锗砌块是一类新颖的高效偶联片段。.目前多数烯炔官能化反应主要针对催化体系的研究，而从新试剂创制角度的关注较少。中国有世界41%的锗储量，申请人关注的Atrane化学在国内特色鲜明，笼状锗的前期探索已获专利支持。申请人在JACS、Angew和Nat.Commun.三个刊物上发表烯炔官能化、交叉偶联的相关一作/通讯论文10篇，具有较好的研究基础。

在该项目的资助下，我们发展了碳笼状锗（Carbagermatrane）作为Atrane家族结构的新成员，基于此完成了Atrane结构锗-硼试剂的合成和结构拓展；针对Atrane结构锗试剂的性质和不饱和体系的官能化发展了一类新颖的重排反应，其产物不仅是多取代烯烃合成的有效sp2偶联模块，同时也可用于构建一类新颖的锗取代N-B有机发光系统。新型锗硼试剂已获得中国专利授权，项目执行期间发表多篇论文，包括J. Am. Chem. Soc. 1篇，Angew. Chem. Int. Ed. 2篇，Chem. Sci. 1篇，Synthesis 1篇，Org. Lett. 1篇；受邀在Synlett撰写Synpacts一篇；此外，在纪念中科院青年创新促进会成立十周年的Chem. Commun.专辑中应邀撰写了主题为Germatranes and carbagermatranes的Feature Article，系统性地总结了我们课题组自成立以来在锗试剂方面开展的工作。