Construction of Acyclic All-Carbon Quaternary Stereocenters and 1,3-Nonadjacent Stereoelements via Organo/Metal Dual Catalyzed Asymmetric Allenylic Substitution of Aldehydes
Construction of Acyclic All-Carbon Quaternary Stereocenters and 1,3-Nonadjacent Stereoelements via Organo/Metal Dual Catalyzed Asymmetric Allenylic Substitution of Aldehydes
复制标题
DOI：
10.1002/anie.202300756
复制
发表时间：
2023-04-07
影响因子：
16.6
通讯作者：
Shao, Zhihui
中科院分区：
文献类型：
--
作者：
Dai, Jun;Li, Long;Shao, Zhihui
通过有机/金属双催化支链和直链醛的不对称烯丙基取代反应，开发了一种未知的无环仲-仲二胺作为有机催化剂，不对称构建功能化的无环全碳季铵立构中心和1，3-非相邻立构单元的方法。虽然人们认为仲-仲二胺很难用作有机/金属双催化中的有机催化剂，但本研究表明，此类二胺可以成功地与金属催化剂结合在有机/金属双催化中。我们的研究使两类重要的图案，这是以前很难访问，轴向手性联烯含无环全碳季立体中心和1，3-不相邻的立体元素轴承联烯基轴向手性和中心手性，在良好的产量与高对映体和非对映体选择性的不对称建设。
A method for the asymmetric construction of functionalized acyclic all-carbon quaternary stereocenters and 1,3-nonadjacent stereoelements has been developed via organo/metal dual catalyzed asymmetric allenylic substitution of branched and linear aldehydes, by developing an unknown acyclic secondary-secondary diamine as the enabling organocatalyst. Although it is believed that secondary-secondary diamines are difficult to be used as the organocatalysts in organo/metal dual catalysis, this study demonstrates that such diamines can be successfully combined with a metal catalyst in organo/metal dual catalysis. Our study enables the asymmetric construction of two important classes of motifs which were previously difficult to access, axially chiral allene-containing acyclic all-carbon quaternary stereocenters and 1,3-nonadjacent stereoelements bearing allenyl axial chirality and central chirality, in good yields with high enantio- and diastereoselectivity.