Supporting data for "Desymmetric Cyanosilylation of Acyclic 1,3-Diketones & Utilization of Transition Metal-1,3-Dicarbonyl Complexes for the Synthesis of Ni(II), Cu(II)-Dibenzotetraaza[14]annulene(DBTAA) Linked Covalent Organic Frameworks (COFs) and Polymers"

The diastereo- and enantioselective creation of vicinal stereocenters from easily accessible starting materials poses a challenge, and the development of acyclic quaternary stereocenters through intermolecular functionalization of linear diketones remains relatively unexplored. The first topic introduces a desymmetric cyanosilylation reaction of acyclic 1,3-diketones. In this study, a bifunctional catalyst derived from dibutyl magnesium and a tetradentate ligand based on pipecolic acid catalyzes an asymmetric cyanosilylation of 1,3-diketones, leading to the formation of vicinal and acyclic tetrasubstituted carbons. This method allows for synthesizing silyl ethers of cyanohydrins with precise stereochemistry and diverse substituents. Additionally, successful demonstrations have been made of converting these compounds into more complex molecules such as heterocycles, triols, and fused rings.The lack of robust linkages and functionalization methods are two obstacles to the development of COFs. Incorporating TM-DBTAA macrocycle into framework materials shows great promise for various applications such as conductive materials, catalysis, and sensors. However, limited methods for synthesizing stable TM-DBTAA-linked COFs hindered the construction of versatile COF structures with functionalized TM-DBTAA linkage. The second topic presents a novel approach to synthesizing TM-DBTAA-linked COFs and polymers, significantly expanding the structural and functional versatility of this valuable material category.<br>

从易得起始原料非对映选择性和对映选择性构建邻位立体中心（vicinal stereocenters）是一项挑战，而通过线性二酮的分子间官能化构建无环季碳立体中心（acyclic quaternary stereocenters）的研究仍相对匮乏。第一个主题介绍了无环1,3-二酮的去对称化氰基硅烷化反应。本研究中，由二丁基镁衍生的双功能催化剂与基于哌啶酸的四齿配体协同作用，催化1,3-二酮的不对称氰基硅烷化反应，形成邻位及无环四取代碳。该方法可合成具有精确立体化学和多样取代基的氰醇硅醚。此外，已成功将这些化合物转化为杂环、三醇和稠环等更复杂的分子。
共价有机框架（Covalent Organic Frameworks，COFs）的发展面临两个障碍：缺乏稳定连接和官能化方法。将TM-DBTAA大环引入框架材料在导电材料、催化和传感器等多种应用中显示出巨大潜力。然而，合成稳定TM-DBTAA连接COFs的方法有限，阻碍了具有功能化TM-DBTAA连接的多功能COF结构的构建。第二个主题提出了一种合成TM-DBTAA连接COFs和聚合物的新颖方法，显著拓展了这一重要材料类别的结构与功能多样性。