Sun Jinwei, Zhou Yongze, Gu Rui, Li Xin, Liu Ao, Zhang Xuan
School of Chemistry and Materials Science, Institute of Advanced Materials and Flexible Electronics (IAMFE), Nanjing University of Information Science and Technology, 219 Ningliu Road, Nanjing, 210044, China.
Nat Commun. 2022 Nov 19;13(1):7093. doi: 10.1038/s41467-022-34901-6.
Transition-metal catalyzed carbosilylation of alkenes using carbon electrophiles and silylmetal (-B, -Zn) reagents as the nucleophiles offers a powerful strategy for synthesizing organosilicones, by incorporating carbon and silyl groups across on C-C double bonds in one step. However, to the best of our knowledge, the study of silylative alkenes difunctionalization based on carbon and silyl electrophiles remains underdeveloped. Herein, we present an example of silylative alkylation of activated olefins with unactivated alkyl bromides and chlorosilanes as electrophiles under nickel catalysis. The main feature of this protocol is employing more easily accessible substrates including primary, secondary and tertiary alkyl bromides, as well as various chlorosilanes without using pre-generated organometallics. A wide range of alkylsilanes with diverse structures can be efficiently assembled in a single step, highlighting the good functionality tolerance of this approach. Furthermore, successful functionalization of bioactive molecules and synthetic applications using this method demonstrate its practicability.
使用碳亲电试剂和硅基金属（-B、-Zn）试剂作为亲核试剂，通过过渡金属催化的烯烃碳硅基化反应，能将碳和硅基一步引入碳-碳双键，为合成有机硅提供了一种强大的策略。然而，据我们所知，基于碳和硅亲电试剂的硅氢化烯烃双官能团化研究仍不充分。在此，我们展示了一个在镍催化下，以未活化的烷基溴和氯硅烷作为亲电试剂，对活化烯烃进行硅氢化烷基化反应的例子。该方法的主要特点是使用更容易获得的底物，包括伯、仲和叔烷基溴以及各种氯硅烷，且无需使用预先制备的有机金属化合物。多种结构各异的烷基硅烷能够在一步反应中高效组装而成，突出了该方法对官能团良好的耐受性。此外，利用这种方法成功实现生物活性分子的官能团化及其合成应用，证明了其实用性。
