Copper-catalyzed rearrangement of (Z)-propynal hydrazones via N-N bond cleavage

Itaru Nakamura; Naozumi Shiraiwa; Ryo Kanazawa; Masahiro Terada

doi:10.1021/ol1017504

Copper-catalyzed rearrangement of (Z)-propynal hydrazones via N-N bond cleavage

Org Lett. 2010 Sep 17;12(18):4198-200. doi: 10.1021/ol1017504.

Authors

Itaru Nakamura¹, Naozumi Shiraiwa, Ryo Kanazawa, Masahiro Terada

Affiliation

¹ 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

PMID: 20718477
DOI: 10.1021/ol1017504

Abstract

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.