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.
