Cyclization reactions of anode-generated amidyl radicals

Area of Science:

• Organic Chemistry
• Electrochemistry
• Computational Chemistry

Background:

• Amidyl radicals are reactive intermediates.
• Electrosynthesis offers mild conditions for generating reactive species.
• Ring formation is a fundamental transformation in organic synthesis.

Purpose of the Study:

• To demonstrate the generation of amidyl radicals via electro-oxidation of amides.
• To investigate the reactivity of amidyl radicals with electron-rich double bonds.
• To explore the formation of five- and six-membered rings using computational methods.

Main Methods:

• Electro-oxidative generation of amidyl radicals from amides.
• Experimental studies on the reaction of amidyl radicals with electron-rich alkenes.
• Density Functional Theory (DFT) calculations using the UB3LYP/6-31G(d,p) level of theory.

Main Results:

• Successful generation of amidyl radicals under mild electro-oxidative conditions.
• Demonstration of amidyl radical addition to electron-rich double bonds.
• Experimental and computational evidence for the formation of five- and six-membered heterocyclic rings.

Conclusions:

• Electro-oxidative generation of amidyl radicals is a viable synthetic method.
• Amidyl radicals are effective synthons for constructing cyclic compounds.
• DFT calculations provide valuable insights into the reaction mechanism and product selectivity.