期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 61, 期 44, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202211596
关键词
Alkenes; Allenes; Asymmetric Catalysis; Axially Chiral Cyclobutenes; [2+2] Cycloaddition
资金
- National Natural Science Foundation of China [22188101, U19A2014]
- Sichuan Science and Technology Program [2021YJ0561]
An efficient catalytic asymmetric [2+2] cycloaddition of allenyl imide and mono- or disubstituted alkenes has been developed. The use of chiral magnesium(II) complex of N,N'-dioxide allows for high yield and excellent enantioselectivity of axially chiral cyclobutenes and four-membered ring-containing spirocycles. This methodology can also be applied for the late-stage modification of biologically active molecules.
An efficient catalytic asymmetric [2+2] cycloaddition of allenyl imide and mono- or disubstituted alkenes is disclosed. The key feature of this method is the use of bidentate allenyl imide and weakly activated and less steric hindered alkene pair by utilizing chiral magnesium(II) complex of N,N '-dioxide, which could provide through-space dispersion interactions to orientate the arrangement of the alkene. This protocol allows the generation of a series of axially chiral cyclobutenes and four-membered ring-containing spirocycles (80 examples) in high yield (up to 99 %) with excellent enantioselectivity (up to >99 % ee), and the late-stage modification of biologically active molecules as well. Experimental studies and DFT calculations revealed that this [2+2] cycloaddition proceeded via a stepwise mechanism involving a short-lived zwitterionic intermediate. The pi-pi interaction between the alkenes and the amide moiety in the ligand was crucial for the enantiocontrol.
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