Han Jixing, Hu Chaopeng, Li Qianli, Liu Liu Leo, Tung Chen-Ho, Cui Ping, Kong Lingbing
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
Department of Chemistry and Research Center for Chemical Biology and Omics Analysis, College of Science, Southern University of Science and Technology, Shenzhen 518055, China.
Inorg Chem. 2023 Nov 20;62(46):18820-18824. doi: 10.1021/acs.inorgchem.3c03232. Epub 2023 Nov 7.
We present the synthesis, structural characterization, and reactivity of alkylideneborane , supported by π-donating N-heterocyclic imino and σ-donating N-heterocyclic carbene (NHC) ligands. The incorporation of these ligands effectively weakens the B═C bond strength, leading to enhanced reactivity. Consequently, selective cleavage of the B═C bond can be achieved using pyridine--oxide, sulfur, and selenium, resulting in the formation of 1,3-dioxa-2,4-diboretane , thioxoborane , and selenoborane , respectively. Furthermore, intriguing B═C bond insertions with CO and CS are observed, affording zwitterionic borenium/fluorenide and dithiaboretane . The former species is readily converted to transient oxoborane and imidazolium enolate, showcasing the bora-Wittig reaction of alkylideneborane. This investigation highlights the potential of alkylideneborane as a versatile building block for synthesizing novel organoboron compounds through unconventional transformations.
我们展示了由π供体N-杂环亚胺和σ供体N-杂环卡宾（NHC）配体支持的亚烷基硼烷的合成、结构表征及反应活性。这些配体的引入有效地削弱了B═C键的强度，从而提高了反应活性。因此，使用吡啶氧化物、硫和硒可实现B═C键的选择性裂解，分别生成1,3-二氧杂-2,4-二硼环戊烷、硫代硼烷和硒代硼烷。此外，还观察到了亚烷基硼烷与CO和CS有趣的B═C键插入反应，生成两性离子硼鎓/芴化物和二硫代硼烷。前一种物质很容易转化为瞬态氧代硼烷和咪唑鎓烯醇盐，展示了亚烷基硼烷的硼-维蒂希反应。这项研究突出了亚烷基硼烷作为一种通用构建单元，通过非常规转化合成新型有机硼化合物的潜力。
