Phosphine-Catalyzed Annulations of 4,4-Dicyano-2-Methylenebut-3-enoates with Maleimides and Maleic Anhydride

A novel phosphine‐catalyzed [4+1] annulation of maleimides with 4,4‐dicyano‐2‐methylenebut‐3‐enoates has been developed to afford spirocyclic products, and the maleimides serves as C1 synthons. Moreover, a phosphine‐catalyzed formal [3+2] annulation between 4,4‐dicyano‐2‐methylenebut‐3‐enoates and m...

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Bibliographic Details
Published in:Angewandte Chemie (International ed.) 2014-09, Vol.53 (40), p.10768-10773
Main Authors: Zhang, Xiao-Nan, Chen, Gen-Qiang, Tang, Xiang-Ying, Wei, Yin, Shi, Min
Format: Article
Language:English
Subjects:
anhydrides
Butyrates - chemistry
Catalysis
Chemical reactions
cyclization
Joint ventures
Maleic anhydride
Maleic Anhydrides - chemistry
Maleimides - chemistry
Organic chemistry
organocatalysis
Phosphines - chemistry
phosphorus
zwitterions
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Summary:A novel phosphine‐catalyzed [4+1] annulation of maleimides with 4,4‐dicyano‐2‐methylenebut‐3‐enoates has been developed to afford spirocyclic products, and the maleimides serves as C1 synthons. Moreover, a phosphine‐catalyzed formal [3+2] annulation between 4,4‐dicyano‐2‐methylenebut‐3‐enoates and maleic anhydride has been also achieved, and maleic anhydride behaved as a C3 synthon in the reaction, thus efficiently affording the functionalized cyclopentenones. A stable phosphinium‐containing zwitterionic compound is the key reactive intermediate in both annulations and was successfully isolated. Plausible mechanisms have been proposed on the basis of control experiments and deuterium‐labeling experiments. Formalities: Novel phosphine‐catalyzed [4+1] and formal [3+2] annulations of 4,4‐dicyano‐2‐methylenebut‐3‐enoates with maleimides and maleic anhydride, respectively, have been developed. Maleimides served as C1 synthons and maleic anhydride behaved as a C3 synthon to afford the corresponding compounds. A phosphinium‐containing zwitterion is the key intermediate in both annulations.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201406100