Zhang Yun, Wang Xi-Chao, Ju Cheng-Wei, Zhao Dongbing
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, 300071, Tianjin, China.
Nat Commun. 2021 Jan 4;12(1):68. doi: 10.1038/s41467-020-20392-w.
1,2-Bis-silyl alkenes have exciting synthetic potential for programmable sequential synthesis via manipulation of the two vicinal silyl groups. Transition metal-catalyzed bis-silylation of alkynes with disilanes is the most straightforward strategy to access such useful building blocks. However, this process has some limitations: (1) symmetric disilanes are frequently employed in most of the reactions to assemble two identical silyl groups, which makes chemoselective differentiation for stepwise downstream transformations difficult; (2) the main catalysts are low-valent platinum group transition metal complexes, which are expensive; and (3) internal alkynes remain challenging substrates with low inherent reactivity. Thus, the development of abundant metal-catalyzed bis-silylation of internal alkynes with unsymmetrical disilanes is of significance. Herein, we solve most of the aforementioned limitations in bis-silylation of unsaturated bonds by developing a strongly coordinating disilane reagent and a Ni(0) catalytic system. Importantly, we sufficiently realize the stepwise recognition of the two silyl groups, making this synthetic protocol of wide potential utility.
1,2-双硅基烯烃通过对两个相邻硅基的操控，在可编程顺序合成方面具有令人兴奋的合成潜力。过渡金属催化的炔烃与乙硅烷的双硅基化反应是获得此类有用结构单元的最直接策略。然而，该过程存在一些局限性：（1）在大多数反应中经常使用对称乙硅烷来组装两个相同的硅基，这使得逐步下游转化的化学选择性区分变得困难；（2）主要催化剂是低价铂族过渡金属配合物，价格昂贵；（3）内炔作为底物，其固有反应性较低，仍然具有挑战性。因此，开发丰富金属催化的内炔与不对称乙硅烷的双硅基化反应具有重要意义。在此，我们通过开发一种强配位乙硅烷试剂和一种Ni(0)催化体系，解决了不饱和键双硅基化反应中上述的大部分局限性。重要的是，我们充分实现了对两个硅基的逐步识别，使这种合成方法具有广泛的潜在用途。
