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Mechanistic investigation of the mechanochemical oxidative amidation of aldehydes

The search for sustainable green technologies with the aim to reduce the disruptive effect of chemical industry on nature has prompted research across the chemical science towards discovery of new environmentally-benign reagents and reaction methodologies. In this context, mechanochemistry or chemistry induced/sustained by application of mechanical force via grinding or milling, has reemerged as a simple, low-cost and energy efficient alternative to classical synthetic procedures. In the recent years, a mechanochemical approach to organic molecules has advanced from a research curiosity to a widespread synthetic technique which enables the implemenation of green chemistry principles into standard laboratory practice. In this contribution, we have investigated the mechanism of oxone- promoted amidation of aldehydes, by means of in situ real-time monitoring of mechanochemical reactions using Raman spectroscopy and quantum chemical DFT calculations. The application of in situ Raman spectroscopy has enabled us to resolve between the two proposed reaction paths, but also provided an insight into the kinetics of intermediate imine formation by substituent effects in aldehydes and amines. The experimental results were supported by DFT calculations of the proposed reaction paths.

mechanochmistry ; reaction mechanism ; oxidative amidation

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