Issue 24, 2021

Mimicking transition metals in borrowing hydrogen from alcohols

Abstract

Borrowing hydrogen from alcohols, storing it on a catalyst and subsequent transfer of the hydrogen from the catalyst to an in situ generated imine is the hallmark of a transition metal mediated catalytic N-alkylation of amines. However, such a borrowing hydrogen mechanism with a transition metal free catalytic system which stores hydrogen molecules in the catalyst backbone is yet to be established. Herein, we demonstrate that a phenalenyl ligand can imitate the role of transition metals in storing and transferring hydrogen molecules leading to borrowing hydrogen mediated alkylation of anilines by alcohols including a wide range of substrate scope. A close inspection of the mechanistic pathway by characterizing several intermediates through various spectroscopic techniques, deuterium labelling experiments, and DFT study concluded that the phenalenyl radical based backbone sequentially adds H+, H˙ and an electron through a dearomatization process which are subsequently used as reducing equivalents to the C–N double bond in a catalytic fashion.

Graphical abstract: Mimicking transition metals in borrowing hydrogen from alcohols

Supplementary files

Article information

Article type
Edge Article
Submitted
24 мар 2021
Accepted
07 май 2021
First published
07 май 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 8353-8361

Mimicking transition metals in borrowing hydrogen from alcohols

A. Banik, J. Ahmed, S. Sil and S. K. Mandal, Chem. Sci., 2021, 12, 8353 DOI: 10.1039/D1SC01681D

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