Yuan Shasha, Zhang Huifang, Qiu Zaozao, Xie Zuowei
School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China.
Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China.
J Org Chem. 2024 Feb 16;89(4):2474-2479. doi: 10.1021/acs.joc.3c02496. Epub 2024 Feb 1.
Picolyl group directed B(3,5)-dialkenylation and B(4)-monoalkenylation of -carboranes has been developed with a very low palladium catalyst loading. The degree of substitution is determined by the cage C(2)-substituents due to steric reasons. On the basis of experimental results, a plausible mechanism is proposed including electrophilic palladation and alkyne insertion followed by protonation.
已开发出在极低钯催化剂负载量下，通过吡啶甲基基团导向实现碳硼烷的B(3,5)-二烯基化和B(4)-单烯基化反应。由于空间位阻原因，取代程度由笼状结构的C(2)-取代基决定。基于实验结果，提出了一个合理的机理，包括亲电钯化、炔烃插入，随后是质子化。
