Duan Meng, Díaz-Oviedo Christian David, Zhou Yang, Chen Xiangyang, Yu Peiyuan, List Benjamin, Houk Kendall N, Lan Yu
Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou, Henan, 450001, China.
Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, 90095, USA.
Angew Chem Int Ed Engl. 2022 Feb 21;61(9):e202113204. doi: 10.1002/anie.202113204. Epub 2022 Jan 14.
Computations and experiments leading to new chiral phosphoric acids (CPAs) for epoxide thionations are reported. Density functional theory calculations reveal the mechanism and origin of the enantioselectivity of such CPA-catalyzed epoxide thionations. The calculated mechanistic information was used to design new efficient CPAs that were tested experimentally and found to be highly effective. Bulky ortho-substituents on the 3,3'-aryl groups of the CPA are important to restrict the position of the epoxide in the key transition states for the enantioselectivity-determining step. Larger para-substituents significantly improve the enantioselectivity of the reaction.
本文报道了用于环氧化合物硫代反应的新型手性磷酸（CPA）的计算和实验研究。密度泛函理论计算揭示了此类CPA催化环氧化合物硫代反应对映选择性的机理和起源。计算得到的机理信息用于设计新型高效的CPA，并通过实验测试发现其非常有效。CPA的3,3'-芳基上的庞大邻位取代基对于在对映选择性决定步骤的关键过渡态中限制环氧化合物的位置很重要。较大的对位取代基可显著提高反应的对映选择性。
