Ma Jin-Tao, Zhang Tianze, Yao Bo-Ying, Xiao Li-Jun, Zhou Qi-Lin
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tianjin 300071, China.
J Am Chem Soc. 2023 Sep 6;145(35):19195-19201. doi: 10.1021/jacs.3c07697. Epub 2023 Aug 24.
We present the first enantioselective nickel-catalyzed borylative coupling of 1,3-dienes with aldehydes, providing an efficient route to highly valuable homoallylic alcohols in a single step. The reaction involves the 1,4-carboboration of dienes, leading to the formation of C-C and C-B bonds accompanied by the construction of two continuous stereogenic centers. Enabled by a chiral spiro phosphine-oxazoline nickel complex, this transformation yields products with exceptional diastereoselectivity, -selectivity, and enantioselectivity. The diastereoselectivity of the reaction can be controlled by employing either ()-1,3-dienes or ()-1,3-dienes.
我们展示了首例镍催化的1,3 - 二烯与醛的对映选择性硼氢化偶联反应，该反应为一步高效合成高价值的高烯丙醇提供了一条途径。该反应涉及二烯的1,4 - 碳硼化，导致形成碳 - 碳键和碳 - 硼键，并同时构建两个连续的手性中心。在手性螺环膦 - 恶唑啉镍配合物的作用下，这种转化产生具有优异非对映选择性、区域选择性和对映选择性的产物。该反应的非对映选择性可以通过使用（+）-1,3 - 二烯或（-）-1,3 - 二烯来控制。
