Enantioselective Palladium(II)-Catalyzed Desymmetrizative Coupling of 7-Azabenzonorbornadienes with Alkynylanilines

Junjie Meng; Hui He; Qianru Liu; Hanhong Xu; Huicai Huang; Shao-Fei Ni; Zhaodong Li

doi:10.1002/anie.202315092

Enantioselective Palladium(II)-Catalyzed Desymmetrizative Coupling of 7-Azabenzonorbornadienes with Alkynylanilines

Angew Chem Int Ed Engl. 2024 Jan 2;63(1):e202315092. doi: 10.1002/anie.202315092. Epub 2023 Nov 28.

Authors

Junjie Meng¹, Hui He², Qianru Liu¹, Hanhong Xu¹, Huicai Huang³, Shao-Fei Ni², Zhaodong Li^{1

4}

Affiliations

¹ National Key Laboratory of Green Pesticide, College of Materials and Energy, South China Agricultural University, Guangzhou, 510641, Guangdong, China.
² Department of Chemistry, Shantou University, Shantou, 515063, Guangdong, China.
³ Key Laboratory of Chinese Medicinal Resource from Lingnan, Ministry of Education, School of Pharmaceutical Sciences, Guangzhou University of Chinese Medicine, Guangzhou, 510641, Guangdong, China.
⁴ National Key Laboratory on Technologies for Chinese Medicine Pharmaceutical Process Control and Intelligent Manufacture, School of Pharmacy, Nanjing University of Chinese Medicine, Nanjing, 210023, Jiangsu, China.

PMID: 37943545
DOI: 10.1002/anie.202315092

Abstract

A Pd^II -catalyzed, domino enantioselective desymmetrizative coupling of 7-azabenzonorbornadienes with alkynylanilines is disclosed herein. This operationally simple transformation generates three covalent bonds and two contiguous stereocenters with excellent enantio- and diastereo-selectivity. The resulting functionalized indole-dihydronaphthalene-amine conjugates served as an appealing platform to streamline the diversity-oriented synthesis (DOS) of other valuable enantioenriched compounds. DFT calculations revealed that the two stabilizing non-covalent interactions contributed to the observed enantioselectivity.

Keywords: Aminopalladation; Asymmetric Synthesis; Desymmetrization; Domino Reactions; Homogeneous Catalysis.

Abstract

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