Copper-catalyzed rearrangement of (Z)-propynal hydrazones via N-N bond cleavage.
Propynal hydrazones are successfully converted to the corresponding 3-aminoacrylonitriles in the presence of copper catalysts in good to high yields. As an example, (Z)-N-(hex-2-ynylidene)morpholin-4-amine reacted in the presence of 10 mol % Cu(OAc)(2) in acetonitrile at 25 °C to afford (E)-3-morpholinohex-2-enenitrile ((E)-2 h) in 77% yield via C-N bond formation and subsequent β-elimination involving cleavage of N-N and C-H bonds.
Nakamura
Itaru
I
Research and Analytical Center for Giant Molecules and Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578 Japan. itaru-n@m.tohoku.ac.jp
Shiraiwa
Naozumi
N
Kanazawa
Ryo
R
Terada
Masahiro
M