Electrochemical defluorinative Matteson-type homologation

Area of Science:

• Organic Chemistry
• Electrochemistry
• Synthetic Methodology

Background:

• The traditional Matteson homologation extends carbon chains via C-B bond insertion, typically involving multiple steps.
• Conventional methods require stringent conditions like cryogenic temperatures and air-sensitive reagents, limiting accessibility.
• Existing protocols for Matteson homologation present challenges in terms of operational complexity and reagent handling.

Purpose of the Study:

• To develop a streamlined, one-pot electrochemical approach to the Matteson homologation.
• To eliminate the need for organolithium reagents and cryogenic conditions in Matteson homologation.
• To broaden the substrate scope by utilizing trifluoromethylarenes as novel carbenoid precursors.

Main Methods:

• Integration of carbanion formation, nucleophilic addition, and boronate rearrangement into a single electrochemical process.
• Utilizing electroreductive defluorination coupled with boronate rearrangement.
• Employing trifluoromethylarenes as carbenoid precursors in the electrochemical Matteson reaction.

Main Results:

• A novel one-pot electrochemical Matteson-type homologation ('e-Matteson') was successfully developed.
• The process circumvents the requirement for organolithium reagents and cryogenic temperatures.
• Trifluoromethylarenes were demonstrated as effective carbenoid precursors for the first time.

Conclusions:

• The developed electrochemical method offers a more accessible and efficient alternative to traditional Matteson homologation.
• This study expands the synthetic utility of the Matteson reaction by introducing a novel precursor class and methodology.
• Mechanistic investigations support the proposed pathway involving boronate formation and rearrangement.