通过钴催化的去对称化[2+2+2]环加成反应对具有全碳季碳中心的吡啶进行对映选择性合成。
Enantioselective Synthesis of Pyridines with All-Carbon Quaternary Carbon Centers via Cobalt-Catalyzed Desymmetric [2+2+2] Cycloaddition.
作者信息
Li Ke, Wei Linsheng, Sun Minghe, Li Bing, Liu Min, Li Changkun
机构信息
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, P. R. China.
出版信息
Angew Chem Int Ed Engl. 2021 Sep 6;60(37):20204-20209. doi: 10.1002/anie.202105452. Epub 2021 Aug 3.
A Co-catalyzed enantioselective desymmetric [2+2+2] cycloaddition for synthesis of pyridines with all-carbon quaternary carbon centers has been developed. The regio- and enantioselectivities are controlled by the inherent nature of terminal alkynes and the substituents on the bisoxazolinephosphine ligands. Pyridines with 5-substitutents could be obtained with >20:1 regioselectivity and up to 94 % ee when terminal alkyl, alkenyl or silyl alkynes and DTBM/Ph-based NPN* ligand L6 were used. Terminal aryl alkynes and Ph/Bn-based ligand L4 leads to formation of pyridines with 6-substitutents in up to 99 % ee.
已开发出一种用于合成具有全碳季碳中心的吡啶的共催化对映选择性去对称[2+2+2]环加成反应。区域选择性和对映选择性由末端炔烃的固有性质和双恶唑啉膦配体上的取代基控制。当使用末端烷基、烯基或硅基炔烃以及基于DTBM/Ph的NPN*配体L6时，可获得区域选择性>20:1且对映体过量高达94%的5-取代吡啶。末端芳基炔烃和基于Ph/Bn的配体L4可导致形成对映体过量高达99%的6-取代吡啶。
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