Oxidation-Triggered Single-Carbon Atom Doping into Acyl Chlorides Using N-Isocyanide

Area of Science:

• Organic Chemistry
• Synthetic Chemistry
• Reaction Mechanisms

Background:

• Atomic carbon is a highly reactive intermediate, challenging to utilize in synthesis due to its transient nature.
• Existing methods for atomic carbon insertion often require high temperatures or metal catalysts, limiting their applicability.

Purpose of the Study:

• To develop a novel, milder method for incorporating atomic carbon into organic molecules.
• To enable the synthesis of cyclic α-chloro ketones from readily available acyl chlorides.

Main Methods:

• Utilized bench-stable N-isocyaniminophosphorane (PINC) as a precursor for atomic carbon generation.
• Employed an oxidation-triggered reaction pathway.
• Conducted mechanistic studies to elucidate the reaction pathway.

Main Results:

• Achieved room temperature synthesis of cyclic α-chloro ketones via carbon-atom insertion into acyl chlorides.
• Demonstrated a new synthetic utility for N-isocyaniminophosphorane (PINC).
• Identified oxidation-induced diazo formation and subsequent carbene generation as key mechanistic steps.

Conclusions:

• The developed method offers a convenient and efficient route to cyclic α-chloro ketones under mild conditions.
• This work expands the synthetic toolbox for utilizing reactive carbon intermediates.
• The mechanistic insights provide a foundation for further development of related transformations.