Additive-controlled chemoselective inter-/intramolecular hydroamination via electrochemical PCET process

Area of Science:

• Organic electrochemistry
• Radical chemistry
• Reaction mechanisms

Background:

• Proton-coupled electron transfer (PCET) is a key mechanism in chemical and biological systems.
• Electrochemical generation of radical species offers a controlled method for initiating reactions.
• Hydroamination reactions are important for synthesizing nitrogen-containing compounds.

Purpose of the Study:

• To investigate the electrochemical generation of amidyl radicals for hydroamination reactions.
• To elucidate the mechanism of these electrochemically driven transformations.
• To explore methods for controlling the chemoselectivity of the hydroamination products.

Main Methods:

• Electrochemistry, specifically cyclic voltammetry (CV), was used to study the radical species.
• The study involved generating amidyl radicals electrochemically.
• Inter- and intramolecular hydroamination reactions were performed and analyzed.

Main Results:

• Distinct inter- and intramolecular hydroamination products were successfully synthesized.
• The chemoselectivity of the reaction was found to depend on the size of a hydrogen bond complex.
• The addition of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) allowed for control over the reaction selectivity.

Conclusions:

• Electrochemically generated amidyl radicals can mediate selective hydroamination reactions.
• The PCET mechanism plays a crucial role in these transformations.
• Hydrogen bonding interactions and additives like HFIP are key factors for controlling reaction outcomes.