State Key Laboratory of Elemento-Organic Chemistry, Department of Chemistry, and Collaborative Innovation Center of Chemical Science and Engineering, Nankai University , Tianjin 300071, China.
J Org Chem. 2014 May 16;79(10):4340-51. doi: 10.1021/jo500158e. Epub 2014 Apr 24.
The pK(a) values of a series of chiral Brønsted acids, including N-triflylphosphoramides, bis(sulfonyl)imides, bis(sulfuryl)imides, dicarboxylic acids, sulfonic acids, and N-phosphinyl phosphoramides, were predicted by using the SMD/M06-2x/6-311++G(2df,2p)//B3LYP/6-31+G(d) method in DMSO. The results revealed that the calculated pKa values ranged from -9.06 to 12.18 for different types of acids. The influence of acidic strength on reactivity and stereoselectivity was discussed using the calculated acidity data. Given that the choice of catalyst with appropriate acidity is the primary condition, several new catalyst candidates were designed by calculating corresponding pK(a) values of parent acids.
用 SMD/M06-2x/6-311++G(2df,2p)//B3LYP/6-31+G(d) 方法在 DMSO 中预测了一系列手性 Brønsted 酸（包括 N-三氟磷酰胺、双（磺酰基）酰亚胺、双（硫代）酰亚胺、二酸、磺酸和 N-膦酰基磷酰胺）的 pK(a) 值。结果表明，不同类型酸的计算 pKa 值范围为-9.06 到 12.18。利用计算得到的酸度数据，讨论了酸性强度对反应性和立体选择性的影响。鉴于选择具有适当酸度的催化剂是首要条件，通过计算母体酸的相应 pK(a) 值，设计了几种新的催化剂候选物。
