Asymmetric Intramolecular Amination Catalyzed with CpIr-SPDO via Nitrene Transfer for Synthesis of Spiro-Quaternary Indolinone

An asymmetric intramolecular spiro-amination to high steric hindering α-C–H bond of 1,3-dicarbonyl via nitrene transfer using inactive aryl azides has been carried out by developing a novel Cp*Ir­(III)-SPDO (spiro-pyrrolidine oxazoline) catalyst, thereby enabling the first successful construction of...

Full description

Saved in:
Bibliographic Details
Published inJournal of the American Chemical Society Vol. 146; no. 28; pp. 18841 - 18847
Main Authors Wei, Shi-Qiang, Li, Zi-Hao, Wang, Shuang-Hu, Chen, Hua, Wang, Xiao-Yu, Gu, Yun-Zhou, Zhang, Ye, Wang, Hong, Ding, Tong-Mei, Zhang, Shu-Yu, Tu, Yong-Qiang
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 17.07.2024
Amer Chemical Soc
Subjects
amination
azides
catalysts
Chemistry
Chemistry, Multidisciplinary
enols
ligands
Physical Sciences
Science & Technology
CROSS-COUPLING REACTIONS
INSERTION
AZIRIDINATION
ACCESS
Online AccessGet full text

Cover

More Information
Summary:An asymmetric intramolecular spiro-amination to high steric hindering α-C–H bond of 1,3-dicarbonyl via nitrene transfer using inactive aryl azides has been carried out by developing a novel Cp*Ir­(III)-SPDO (spiro-pyrrolidine oxazoline) catalyst, thereby enabling the first successful construction of structurally rigid spiro-quaternary indolinone cores with moderate to high yields and excellent enantioselectivities. DFT computations support the presence of double bridging H–F bonds between [SbF6]− and both the ligand and substrate, which favors the plane-differentiation of the enol π-bond for nitrenoid attacking. These findings open up numerous opportunities for the development of new asymmetric nitrene transfer systems.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/jacs.4c05560