Synthesis of Axially Chiral QUINAP Derivatives by Ketone-Catalyzed Enantioselective Oxidation
Peng-Ying Jiang
Harbin Institute of Technology, Harbin, 150001 China
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 China
Search for more papers by this authorDr. San Wu
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 China
Search for more papers by this authorDr. Guan-Jun Wang
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 China
Search for more papers by this authorCorresponding Author
Dr. Shao-Hua Xiang
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Bin Tan
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 China
Search for more papers by this authorPeng-Ying Jiang
Harbin Institute of Technology, Harbin, 150001 China
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 China
Search for more papers by this authorDr. San Wu
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 China
Search for more papers by this authorDr. Guan-Jun Wang
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 China
Search for more papers by this authorCorresponding Author
Dr. Shao-Hua Xiang
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Bin Tan
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 China
Search for more papers by this authorAbstract
QUINAPs have emerged as a pivotal class of axially chiral compounds with remarkable features in the stereoinduction of diverse enantioselective transformations. However, the confined substrate range and extravagant price still pose challenges, limiting their broader utilization. Herein, we describe the first atroposelective oxidation of an N atom using a chiral ketone catalyst, allowing the kinetic resolution of QUINAPOs to give both the unreacted substrates and their corresponding N-oxides with excellent enantioselectivity. Importantly, the enantioenriched products can be readily converted into the QUINAP targets without any loss of stereochemical integrity. Mechanistic investigations indicate that a dioxirane, generated through the oxidation of the ketone with oxone, acts as the active catalytic species. Furthermore, we have successfully extended this catalytic system to the kinetic resolution of QUINOLs and the dynamic kinetic transformation of pyridine analogues of QUINAPO possessing a labile stereogenic axis. The practicality of the developed protocol is further demonstrated by the successful application of QUINAPO N-oxide as a Lewis base catalyst in a series of enantioselective transformations.
Open Research
Data Availability Statement
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