Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Rd, 200032, Shanghai, China.
Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China.
Nat Commun. 2021 Dec 8;12(1):7146. doi: 10.1038/s41467-021-27441-y.
The asymmetric synthesis of chiral-at-cage o-carboranes, whose chirality is associated with the substitution patterns on the polyhedron, is of great interest as the icosahedral carboranes have wide applications in medicinal and materials chemistry. Herein we report an intermolecular Ir-catalyzed enantioselective B-H alkenylation for efficient and facile synthesis of chiral-at-cage o-carboranes with new skeletons under mild reaction conditions. Generally very good to excellent yields with up to 99% ee can be achieved in this Ir-catalyzed B-H alkenylation. The enantiocontrol model is proposed based on Density Functional Theory calculations in which the use of chiral phosphoramidite ligand is essential for such asymmetric o-carborane B-H alkenylation.
笼状手性 o-碳硼烷的不对称合成具有重要意义，因为其手性与多面体上的取代模式有关，而笼状 o-碳硼烷在药物和材料化学中有广泛的应用。在此，我们报道了一种分子间 Ir 催化的对映选择性 B-H 烯基化反应，可在温和的反应条件下高效、简便地合成具有新骨架的笼状手性 o-碳硼烷。在 Ir 催化的 B-H 烯基化反应中，通常可以获得非常好到优秀的产率，最高可达 99%ee。基于密度泛函理论计算提出了对映控制模型，其中手性膦酰胺配体的使用对于这种不对称 o-碳硼烷 B-H 烯基化反应是必不可少的。
