Enantioselective Trapping of Pd-Containing 1,5-Dipoles by Photogenerated Ketenes: Access to 7‑Membered Lactones Bearing Chiral Quaternary Stereocenters

An enantioselective [5+2] cycloaddition of vinylethylene carbonates and α-diazoketones was achieved for the first time by merging photoactivation and asymmetric Pd catalysis. The key to the success of this method is the enantioselective trapping of Pd-containing, 1,5-dipolar intermediates by ketenes...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2019-01, Vol.141 (1), p.133-137
Main Authors: Wei, Yi, Liu, Song, Li, Miao-Miao, Li, Yi, Lan, Yu, Lu, Liang-Qiu, Xiao, Wen-Jing
Format: Article
Language:English
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Summary:An enantioselective [5+2] cycloaddition of vinylethylene carbonates and α-diazoketones was achieved for the first time by merging photoactivation and asymmetric Pd catalysis. The key to the success of this method is the enantioselective trapping of Pd-containing, 1,5-dipolar intermediates by ketenes, a class of reactive C2 synthons, which were generated in an in situ and traceless manner under visible light irradiation. Through this trapping, a variety of 7-membered lactones bearing challenging chiral quaternary stereocenters can be accessed in a facile manner with good efficiency and high enantioselectivity (up to 99% yield and 96:4 er).
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.8b12095