Regio‐ and Atroposelective Ring‐Opening of 1H‐Benzooxazolopyridinones

• Published in: Angewandte Chemie International Edition 2024-04, Vol.63 (17)
• Main Authors: Deng, Ruixian, Dong, Puyang, Ge, Jimeng, Zhang, Wenjing, Xue, Xiaoping, Duan, Longhui, Shi, Linlin, Gu, Zhenhua
• Format: Article
• Language: English
• Subjects: Chemical synthesis; Enantiomers; Ethers; Natural products; Nickel; Phosphine; Phosphines; Regioselectivity; Stereoselectivity
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202402231

The development of new methods for regio‐ and stereoselective activation of C−O bonds in ethers holds significant promise for synthetic chemistry, offering advantages in terms of environmental sustainability and economic efficiency. Moreover, the C−N atropisomers represent a fascinating and crucial chiral system, extensively found in natural products, pharmaceutical leads, and the frameworks of advanced materials. In this work, we have introduced a nickel‐catalyzed regio‐ and enantioselective carbon‐oxygen arylation reaction for atroposelective synthesis of N‐arylisoquinoline‐1,3(2H,4H)‐diones. The high regioselectivity of C−O cleavage benefits from the high stability of the in situ formed (amido)ethenolate via oxidative addition. Additionally, the self‐activation of the aryl C−O bond facilitates the reaction under mild conditions, leading to outstanding enantioselectivities. The diverse post‐functionalizations of the axially chiral isoquinoline‐1,3(2H,4H)‐diones further highlighted the utility of this protocol in preparing valuable C−N atropisomers, including the chiral phosphine ligands.