Synthesis of Axially Chiral QUINAP Derivatives by Ketone-Catalyzed Enantioselective Oxidation

Jiang, Peng-Ying1,2; Wu, San2; Wang, Guan-Jun2; Xiang, Shao-Hua2; Tan, Bin2

2023-08-25

10.1002/anie.202309272

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Impact Factor & Quartile

1433-7851

1521-3773

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.

(Dynamic) Kinetic Resolution Axial Chirality Enantioselective Oxidation Ketone Catalysis QUINAP Derivatives

SCI

English

NI Journal Papers

Corresponding

We are grateful for financial support from the National Key Ramp;amp;D Program of China (2022YFA1503703, 2021YFF0701604), the National Natural Science Foundation of China (22231004, 21825105, 22271135), Guangdong Innovative Program (2019BT02Y335), and She["2022YFA1503703","2021YFF0701604"] ; National Key Ramp;amp;D Program of China["22231004","21825105","22271135"] ; National Natural Science Foundation of China[2019BT02Y335] ; Guangdong Innovative Program["KQTD20210811090112004","JCYJ20210324120205016","JCYJ20210324105005015"]

Chemistry

Chemistry, Multidisciplinary

WOS:001060729600001

WILEY-V C H VERLAG GMBH

CHEMISTRY

Web of Science

1.Harbin Inst Technol, Harbin 150001, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Dept Chem, Shenzhen 518055, Peoples R China

Jiang, Peng-Ying,Wu, San,Wang, Guan-Jun,et al. Synthesis of Axially Chiral QUINAP Derivatives by Ketone-Catalyzed Enantioselective Oxidation[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2023.

Jiang, Peng-Ying,Wu, San,Wang, Guan-Jun,Xiang, Shao-Hua,&Tan, Bin.(2023).Synthesis of Axially Chiral QUINAP Derivatives by Ketone-Catalyzed Enantioselective Oxidation.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION.

Jiang, Peng-Ying,et al."Synthesis of Axially Chiral QUINAP Derivatives by Ketone-Catalyzed Enantioselective Oxidation".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2023).