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Enantio- and Diastereodivergent Construction of 1,3-Nonadjacent Stereocenters Bearing Axial and Central Chirality through Synergistic Pd/Cu Catalysis
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2021-08-05 , DOI: 10.1021/jacs.1c05087
Jiacheng Zhang 1 , Xiaohong Huo 1 , Junzhe Xiao 2 , Ling Zhao 1 , Shengming Ma 2, 3 , Wanbin Zhang 1
Affiliation  

In contrast to the widely explored methods for the asymmetric synthesis of molecules bearing a single stereocenter or adjacent stereocenters, the concurrent construction of 1,3-stereogenic centers in an enantio- and diastereoselective manner remains a challenge, especially in acyclic systems. Herein, we report an enantio- and diastereodivergent construction of 1,3-nonadjacent stereocenters bearing allenyl axial and central chirality through synergistic Pd/Cu-catalyzed dynamic kinetic asymmetric allenylation with racemic allenylic esters. The protocol is suitable for a wide range of substrates including the challenging allenylic esters with less sterically bulky substituents and provided chiral allenylic products bearing 1,3-nonadjacent stereocenters with high levels of enantio- and diastereoselectivities (up to >20:1 dr and >99% ee). Furthermore, several representative transformations involving axial-to-central chirality transfer were conducted, affording useful structural motifs containing nonadjacent stereocenters in a diastereodivergent manner.

中文翻译:

通过协同 Pd/Cu 催化构建具有轴向和中心手性的 1,3-非相邻立体中心的对映和非对映发散结构

与广泛探索的用于不对称合成具有单个立体中心或相邻立体中心的分子的方法相比,以对映和非对映选择性方式同时构建 1,3-立体中心仍然是一个挑战,尤其是在无环系统中。在此,我们报告了通过与外消旋烯丙酯协同作用的 Pd/Cu 催化动态动力学不对称烯丙基化,构建了具有烯基轴向和中心手性的 1,3-非相邻立体中心的对映和非对映发散结构。该协议适用于广泛的底物,包括具有较小空间体积取代基的具有挑战性的烯丙酯,并提供具有高水平对映选择性和非对映选择性(高达 >20:1 dr 和 > 99% ee)。
更新日期:2021-08-19
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