Latvian Institute of Organic Synthesis, Aizkraukles 21, Riga LV-1006, Latvia.
Department of Chemistry, University of Latvia, Jelgavas 1, Riga LV-1004, Latvia.
J Org Chem. 2021 May 21;86(10):7189-7202. doi: 10.1021/acs.joc.1c00545. Epub 2021 May 11.
Non-enzymatic dynamic kinetic resolution (DKR) of secondary alcohols by enantioselective acylation using an isothiourea-derived HyperBTM catalyst and racemization of slowly reacting alcohol by Bäckvall's ruthenium complex is reported. The DKR approach features high enantioselectivities (up to 99:1), employs easy-to-handle crystalline 4-nitrophenyl isobutyrate as the acylating reagent, and proceeds at room temperature and under an ambient atmosphere. The stereoinduction model featuring cation-π system interactions between the acylated HyperBTM catalyst and π electrons of an alcohol aryl subunit has been elaborated by DFT calculations.
报道了通过使用异硫脲衍生的 HyperBTM 催化剂对仲醇进行对映选择性酰化的非酶动态动力学拆分（DKR），以及缓慢反应醇的外消旋化反应通过 Backvall 的钌配合物。DKR 方法具有高对映选择性（高达 99:1），使用易于处理的结晶 4-硝基苯基异丁酸酯作为酰化试剂，并在室温下、在环境气氛中进行。通过 DFT 计算详细阐述了酰化 HyperBTM 催化剂与醇芳基部分的π电子之间的阳离子-π 体系相互作用的立体诱导模型。
