Unilever Centre for Molecular Science Informatics, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
J Org Chem. 2013 Sep 6;78(17):8796-801. doi: 10.1021/jo401611q. Epub 2013 Aug 26.
1,1'-Bi-2-naphthol (BINOL)-derived catalysts catalyze the asymmetric propargylation of ketones. Density functional theory (DFT) calculations show that the reaction proceeds via a closed six-membered transition structure (TS) in which the chiral catalyst undergoes an exchange process with the original cyclic boronate ligand. This leads to a Lewis acid type activation mode, not a Brønsted acid process, which accurately predicts the stereochemical outcome observed experimentally.
1,1'-联萘酚（BINOL）衍生的催化剂可以催化酮的不对称丙炔化反应。密度泛函理论（DFT）计算表明，反应通过一个封闭的六元过渡态（TS）进行，其中手性催化剂与原始环状硼酸酯配体发生交换过程。这导致了路易斯酸类型的活化模式，而不是布朗斯台德酸过程，这准确地预测了实验中观察到的立体化学结果。
