Li Jianhua, Jiang Chao
School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, Jiangsu 210094, China.
Org Lett. 2021 Jul 16;23(14):5359-5362. doi: 10.1021/acs.orglett.1c01678. Epub 2021 Jun 29.
A palladium-catalyzed β-C(sp)-H silylation of aliphatic ketones with disilanes to afford β-silyl ketones is reported. The aminooxyamide auxiliary is critical for the C-H activation and silylation. The reaction tolerates a number of functional groups and shows good selectivity in silylating β-C(sp)-H bonds in the company of C(sp)-H bonds and acidic α-C(sp)-H bonds. The reaction is scalable, and the aminooxyamide auxiliary is readily removed to give β-silyl ketones, which could serve as useful building blocks for organic synthesis. Late-stage diversification using this protocol is demonstrated in the silylation of santonin with good yield.
报道了一种钯催化脂肪族酮与乙硅烷的β-C(sp)-H硅基化反应，以生成β-硅基酮。氨氧基酰胺助剂对C-H活化和硅基化至关重要。该反应能耐受多种官能团，并且在硅基化β-C(sp)-H键时，对C(sp)-H键和酸性α-C(sp)-H键具有良好的选择性。该反应可扩大规模，且氨氧基酰胺助剂易于除去以得到β-硅基酮，β-硅基酮可作为有机合成的有用砌块。利用该方法进行的后期多样化反应在山道年的硅基化反应中得到了验证，产率良好。
