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Oxidative C-H activation of amines using protuberant lychee-like goethite
Citation:
Verma, S., R. Baig, M. Nadagouda, AND R. Varma. Oxidative C-H activation of amines using protuberant lychee-like goethite. Scientific Reports. Nature Publishing Group, London, Uk, 8:2024, (2018). https://doi.org/10.1038/s41598-018-20246-y
Impact/Purpose:
There is strong interest in developing new sustainable and low cost methods of synthesizing industrial chemicals. C-H Activation is of considerable current interest because it has the potential of becoming a transforming strategic reaction. The methods described take oxygen from air to be used as an oxidant. This research would be relevant to those interested in sustainable green chemistry practices.
Description:
Goethite with protuberant lychee morphology has been synthesized that accomplishes C-H activation of N-methylanilines to generate α-aminonitriles; the catalyst takes oxygen from air and uses it as a cooxidant in the process. Inspired by nature, we aspired to design a protocol for the C-H activation of amines using one of the most benign and abundant metals in the earth’s crust, iron. The ultimate success of this chemistry lies in the use of atmospheric oxygen in air as a replacement for the hazardous oxidants which include hydrogen peroxide and organic peracids. In spite of burgeoning interest in this area, there are few reports available on this topic; Murahashi group utilized molecular oxygen as an oxidant in the presence of ruthenium salt whereas Fu and co-workers used a catalytic amount of radical initiator (Azobisisobutyronitrile) AIBN. Homogenousvanadium and iron-based catalysts were also reported for the same reaction. Recently, a heterogeneous ruthenium-based photocatalyst was used for the synthesis of α-aminonitriles under visible light irradiation. However, to date none of the reports demonstrate the use of atmospheric oxygen for this reaction. The use of earth-abundant base metals and eco-friendly oxidants define the economic aspects and environmental impacts that are directly linked to the reaction pathway, atom economy and waste generation. All of these limitations could possibly be addressed by replacing often deployed transition metals with benign ferrites and typical noxious oxidants with air. Success in this domain will address the growing economic and environmental concerns associated with a chemical synthesis. In this article, we present the outcome of our extensive exploratory work and experimentation leading to the discovery of a special morphological version of ferrites. We also address the stoichiometric needs for them to perform the C-H activation of amines under simple aerial atmosphere.
URLs/Downloads:
DOI: Oxidative C-H activation of amines using protuberant lychee-like goethite
http://www.nature.com/articles/s41598-018-20246-y
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