Assessing counterion effects in gold-catalyzed domino spirocyclization: an industrial perspective on hydrogen bonding
1Institute for Chemical Physics & Department of Chemistry, School of Science, State Key Laboratory of Electrical Insulation and Power Equipment & MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Xi'an Jiaotong University, Xi'an 710049, China. xzhao@mail.xjtu.edu.cn.
Abstract:
We herein report a computational study of the hydrogen bonding in gold-catalyzed ipso-cyclization to diverse polyheterocyclic frameworks. The different roles of these hydrogen bonds are analyzed for the different ipso-cyclization reactions. The fine-tunability of the electronic as well as steric properties of gold counterions contributed substantially to the popularity of the dearomatization reaction, with robust applications in total synthesis and gold catalysis. We have found correlation between the hydrogen bonding parameters and chemoselectivity in gold-catalyzed spirocyclization, playing critical roles in determining the reaction direction of counterion-based enantioselective gold catalysis. The expanded use of counterions via hydrogen bonding interaction can occupy an important role in the future concerning catalyst optimization in gold catalysis.
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