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Straightforward Synthesis of 1,2‐Dicyanoalkanes from Nitroalkenes and Silyl Cyanide Mediated by Tetrabutylammonium Fluoride
Author(s) -
Kiyokawa Kensuke,
Nagata Takaya,
Hayakawa Junpei,
Minakata Satoshi
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201404780
Subject(s) - hypervalent molecule , silylation , tetrabutylammonium fluoride , chemistry , cyanide , fluoride , trimethylsilyl cyanide , substrate (aquarium) , trimethylsilyl , tandem , organic chemistry , combinatorial chemistry , inorganic chemistry , catalysis , reagent , materials science , oceanography , composite material , geology
A straightforward synthesis of 1,2‐dicyanoalkanes by reacting nitroalkenes with trimethylsilyl cyanide in the presence of tetrabutylammonium fluoride is described. The reaction proceeds through a tandem double Michael addition under mild conditions. Employing the hypervalent silicate generated from trimethylsilyl cyanide and tetrabutylammonium fluoride is essential for achieving this transformation. Mechanistic studies suggest that a small amount of water included in the reaction media plays a key role. This protocol is applicable to various types of substrates including electron‐rich and electron‐deficient aromatic nitroalkenes, and aliphatic nitroalkenes. Moreover, vinyl sulfones were found to be good alternatives, particularly for electron‐deficient nitroalkenes. The broad substrate scope and functional group tolerance of the reaction makes this approach a practical method for the synthesis of valuable 1,2‐dicyanoalkanes.