Liu Xun-Shen, Tang Zhiqiong, Si Zhi-Yao, Zhang Zhikun, Zhao Lei, Liu Lu
School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, P. R. China.
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, East China Normal University, 3663N Zhongshan Road, Shanghai, 200062, P. R. China.
Angew Chem Int Ed Engl. 2022 Oct 4;61(40):e202208874. doi: 10.1002/anie.202208874. Epub 2022 Aug 24.
An asymmetric para-C(sp )-H bond functionalization of alkyl benzene derivatives was successfully developed via cooperative catalysis of gold and chiral phosphoric acid (CPA), leading to synthetically useful chiral 1,1-diaryl motifs. Chiral phosphoric acid, ligand, and molecular sieves were found to be crucial for enantioselectivity control of this transformation. The salient features of this protocol include mild conditions, high efficiency, commercially available starting materials, highly chemo- and site- as well as enantioselective aromatic C-H functionalization, broad substrate scope, and extensive applications of the chiral products. The mechanistic studies suggested that two CPAs might be involved in chiral induction.
通过金和手性磷酸（CPA）的协同催化，成功开发了一种烷基苯衍生物的不对称对C(sp )-H键官能团化反应，得到了具有合成价值的手性1,1-二芳基结构单元。发现手性磷酸、配体和分子筛对于该转化的对映选择性控制至关重要。该方法的显著特点包括温和的条件、高效率、商业可得的起始原料、高度的化学选择性、位点选择性以及对映选择性芳香C-H官能团化、广泛的底物范围和手性产物的广泛应用。机理研究表明，两个CPA可能参与了手性诱导。
