Institute for Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University Jena, Humboldtstrasse 10, 07743, Jena, Germany.
Current address: School of Chemistry and Chemical Engineering, Nantong University, 226019, Nantong, Jiangsu, China.
Chemistry. 2023 Jul 3;29(37):e202300641. doi: 10.1002/chem.202300641. Epub 2023 May 9.
Lewis base catalyzed allylations of C-centered nucleophiles have been largely limited to the niche substrates with acidic C-H substituted for C-F bonds at the stabilized carbanionic carbon. Herein we report that the concept of latent pronucleophiles serves to overcome these limitations and allow for a variety of common stabilized C-nucleophiles, when they are introduced as the corresponding silylated compounds, to undergo enantioselective allylations using allylic fluorides. The reactions of silyl enol ethers afford the allylation products in good yields and with high degree of regio/stereoselectivity as well as diastereoselectivity when cyclic silyl enol ethers are used. Further examples of silylated stabilized carbon nucleophiles that undergo efficient allylation speak in favor of the general applicability of this concept to C-centered nucleophiles.
Lewis 碱催化的 C 中心亲核试剂的烯丙基化反应在很大程度上仅限于具有酸性 C-H 取代 C-F 键的稳定碳负离子碳的利基底物。在此，我们报告说，潜伏亲核试剂的概念可用于克服这些限制，并允许各种常见的稳定 C-亲核试剂，当它们作为相应的硅烷化化合物引入时，使用烯丙基氟化物进行对映选择性烯丙基化反应。硅基烯醇醚的反应以良好的收率和高区域/立体选择性以及环状硅基烯醇醚使用时的非对映选择性提供了烯丙基化产物。进一步的硅化稳定碳亲核试剂的例子表明，该概念对 C 中心亲核试剂具有普遍适用性。
