Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
J Org Chem. 2022 Aug 5;87(15):10054-10061. doi: 10.1021/acs.joc.2c01039. Epub 2022 Jul 18.
Current models for oxazaborolidine-catalyzed transition-state structures are determined by C-H···O-B and C-H···O═S formyl hydrogen bonding between the electrophile and catalyst. However, selectivity in the oxazaborolidine-catalyzed Mukaiyama aldol cannot be fully rationalized using these models. Combined density functional theory and noncovalent interaction analyses reveal a new reaction model relying on C-H···O, C-H···π, and π-π interactions between the nucleophile, electrophile, and catalyst to induce selectivity.
目前，氧杂硼烷催化过渡态结构的模型是通过亲电试剂和催化剂之间的 C-H···O-B 和 C-H···O═S 甲酰氢键来确定的。然而，这些模型并不能完全解释氧杂硼烷催化的 Mukaiyama 羟醛缩合的选择性。结合密度泛函理论和非共价相互作用分析，揭示了一种新的反应模型，该模型依赖于亲核试剂、亲电试剂和催化剂之间的 C-H···O、C-H···π 和 π-π 相互作用来诱导选择性。
