Beijing National Laboratory for Molecular Sciences, College of Chemistry, Peking University, Beijing, 100871, China.
Org Biomol Chem. 2012 Feb 28;10(8):1537-42. doi: 10.1039/c2ob06941e. Epub 2012 Jan 5.
The first transition-metal-catalyzed activation of silyl C(sp(3))-H bond was realized and synthetically applied. A variety of organic skeletons substituted with SiMe(3) groups could undergo the Pd-catalyzed intramolecular coupling reaction, resulting in an unprecedented synthetic method for yielding six-membered silacycles. It was found that the adjacent Si atom played an essential role for the activation of the C(sp(3))-H bond of the SiMe(3) group; no activation reaction of the C(sp(3))-H bond of the CMe(3) group took place under the same reaction conditions.
首次实现了首例过渡金属催化的硅烷基 C(sp(3))-H 键的活化，并将其应用于合成。各种取代有 SiMe(3)基团的有机骨架都可以进行 Pd 催化的分子内偶联反应，为生成六元硅杂环提供了一种前所未有的合成方法。研究发现，相邻的 Si 原子对于 SiMe(3)基团的 C(sp(3))-H 键的活化起着至关重要的作用；在相同的反应条件下，CMe(3)基团的 C(sp(3))-H 键没有发生活化反应。
