Ramesh Perla, Sreenivasulu Chinnabattigalla, Kishore Dakoju Ravi, Srinivas Dasari, Gorantla Koteswara Rao, Mallik Bhabani S, Satyanarayana Gedu
Department of Chemistry, Indian Institute of Technology, Hyderabad, Sangareddy, Kandi, Telangana 502 285, India.
J Org Chem. 2022 Mar 4;87(5):2204-2221. doi: 10.1021/acs.joc.1c02865. Epub 2022 Feb 10.
This article describes the development of a new aliphatic nitrile-template-directed remote -selective C-H olefin functionalization reaction of arenes. Remarkably, unlike the previous reports, this process is feasible at room temperature and enabled the formation of products with excellent regioselectivity. The present protocol encompasses a broad spectrum of substituted dihydrocinnamic acids and olefins, producing -C-H olefinated products (up to 96% yield). In addition, the efficacy of the present method has been showcased by the synthesis of various drug analogues (e.g., cholesterol, estrone, ibuprofen, and naproxen). Significantly, the robustness of -olefination was also demonstrated by gram-scale synthesis. The new nitrile-based -directing template, in particular, could be easily synthesized in two steps and recycled under mild conditions.
本文描述了一种新型脂肪族腈模板导向的芳烃远程选择性C-H烯烃官能团化反应的发展。值得注意的是，与之前的报道不同，该过程在室温下可行，并能形成具有优异区域选择性的产物。本方案涵盖了广泛的取代二氢肉桂酸和烯烃，生成了-C-H烯烃化产物（产率高达96%）。此外，通过合成各种药物类似物（如胆固醇、雌酮、布洛芬和萘普生）展示了本方法的有效性。重要的是，克级合成也证明了-烯烃化的稳健性。特别是，新型腈基导向模板可以很容易地通过两步合成，并在温和条件下循环使用。
