Desymmetric Cyanosilylation of Acyclic 1,3-Diketones.
Pan XuChang ShenAiqing XuKam-Hung LowZhongxing HuangPublished in: Angewandte Chemie (International ed. in English) (2022)
Diastereo- and enantioselective construction of vicinal stereocenters from easily available starting materials is a challenging task. Here, we report that a bifunctional catalyst prepared from dibutylmagnesium and a pipecolinol-derived tetradentate ligand can enable an asymmetric cyanosilylation of 1,3-diketones to forge a pair of neighboring and acyclic tetrasubstituted carbons. The high stereoselectivity results from the rigid conformation of the diketone in the catalyst pocket, where the Lewis acidic magnesium center, together with the free hydroxyl group as a putative hydrogen bond donor, bind with both carbonyls. Consequently, stereochemically well-defined cyanohydrin silyl ethers with a diverse collection of substituents were prepared. Their rapid derivatization to molecules of higher complexity, such as heterocycles, triols, and fused rings, were also demonstrated.
Keyphrases
- ionic liquid
- highly efficient
- metal organic framework
- visible light
- room temperature
- reduced graphene oxide
- carbon dioxide
- ms ms
- high performance liquid chromatography
- liquid chromatography tandem mass spectrometry
- gas chromatography mass spectrometry
- molecular dynamics simulations
- simultaneous determination
- tandem mass spectrometry
- liquid chromatography
- gold nanoparticles
- solid phase extraction
- crystal structure
- solid state