Zhang, Guoxiang Yang, Shuang Zhang, Xiaoyan Lin, Qiqiao Das, Deb. K. Liu, Jian Fang, Xinqiang Dynamic Kinetic Resolution Enabled by Intramolecular Benzoin Reaction: Synthetic Applications and Mechanistic Insights The highly enantio-, diastereo-, and regioselective dynamic kinetic resolution of β-ketoesters and 1,3-diketones was achieved via a chiral <i>N</i>-heterocyclic carbene catalyzed intramolecular cross-benzoin reaction. A variety of tetralone derivatives bearing two contiguous stereocenters and multiple functionalities were liberated in moderate to excellent yields and with high levels of stereoselectivity (>95% ee and >20:1 dr in most cases). In addition, the excellent regioselectivity control for aryl/alkyl 1,3-diketones, and the superior electronic differentiation of 1,3-diarylketones were highlighted. Moreover, a set of new mechanistic rationale that differs with the currently widely accepted understanding of intramolecular benzoin reactions was established to demonstrate the superior preference of benzoin over aldol transformation: (1) A coexistence of competitive aldol and benzoin reactions was detected, but a retro-aldol-irreversible benzoin process performs a vital role in the generation of predominant benzoin products. (2) The most essential role of an <i>N</i>-electron-withdrawing substituent in triazolium catalysts was revealed to be accelerating the rate of the benzoin transformation, rather than suppressing the aldol process through reducing the inherent basicity of the catalyst. benzoin transformation;benzoin products;chiral N;tetralone derivatives;Mechanistic Insights;benzoin reactions;regioselectivity control;intramolecular benzoin reactions;triazolium catalysts;Dynamic Kinetic Resolution Enabled;heterocyclic carbene;Synthetic Applications;aldol transformation;Intramolecular Benzoin Reaction;aldol process 2016-06-07
    https://acs.figshare.com/articles/dataset/Dynamic_Kinetic_Resolution_Enabled_by_Intramolecular_Benzoin_Reaction_Synthetic_Applications_and_Mechanistic_Insights/3438812
10.1021/jacs.6b02929.s002