Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
J Org Chem. 2020 Dec 4;85(23):15449-15456. doi: 10.1021/acs.joc.0c02226. Epub 2020 Nov 23.
The mechanism of the asymmetric BINOL-derived hydroxyl carboxylic acid catalyzed allylboration of benzaldehyde was investigated using density functional theory calculations. A new reaction model is proposed, and the roles of the two Brønsted acidic sites of the catalyst elucidated. Catalyst distortion was found to be a key factor in determining stereoselectivity. The flexibility of the hydroxyl carboxylic acid catalyst leads to significant differences in the mechanism and origins of selectivity compared to the equivalent phosphoric acid catalyzed reaction.
采用密度泛函理论计算研究了不对称 BINOL 衍生的羟基羧酸催化苯甲醛烯丙基硼化的反应机理。提出了一个新的反应模型，并阐明了催化剂中两个 Brønsted 酸性位的作用。发现催化剂变形是决定立体选择性的关键因素。与等效的磷酸催化反应相比，羟基羧酸催化剂的灵活性导致反应机理和选择性起源有很大差异。
