Masuda R,
Yasukawa T,
*,
Yamashita Y,
Maki T,
Yoshida T,
Kobayashi S.
*
The University of Tokyo, Japan
Heterogeneous Single-Atom Zinc on Nitrogen-Doped Carbon Catalyzed Electrochemical Allylation of Imines.
J. Am. Chem. Soc. 2023;
145: 11939-11944
DOI:
10.1021/jacs.3c03674
Key words
electrochemical allylation - imines - zinc - nitrogen-doped carbon
Significance
Single-atomic zinc supported on nitrogen-doped carbon (Zn–N–C/HCl) was prepared by calcination of a zeolite imidazolate framework-8 (ZIF-8) followed by HCl aq treatment (eq. 1). Zn–N–C/HCl, fixed on a cathode, catalyzed the electrochemical allylation of the imines with allyl bromides to give the corresponding homoallylic amines in up to 99% yield (eq. 2). Benzaldehyde also underwent the allylation with allyl bromide in 96% yield (eq. 3).
Comment
Zinc-leaching from the cathode was suppressed to 1.2–3.5 mol% under the allylation conditions. The electrochemical allylation of benzylideneaniline with allyl bromide was also carried out under continuous-flow conditions over 50 hours, where the turnover number (TON) of Zn–N–C/HCl was 9.0 and Zn-leaching was <2 mol%.
