A recent research work from Prof. LYU Hairong’s group has been published in Nature, titled “Electrochemical defluorinative Matteson-type homologation reaction.”
The Matteson homologation, first developed by Matteson in 1980, involves the formal insertion of a one-carbon unit into a carbon-boron bond. Since its discovery, this name reaction has become a widely explored and applied “atom-by-atom” strategy in synthetic chemistry, playing a critical role in the iterative construction of carbon chains, natural product synthesis, and small-molecule drug development. However, its broader practical applications have been significantly limited due to the reliance on highly sensitive organolithium reagents, cryogenic conditions, and labor-intensive three-step procedures.
In this work, Prof. Lyu’s group reported an “e-Matteson” homologation, which integrates the three transformations of the classic Matteson reaction into a one-pot electrochemical process. This approach combines electroreductive defluorination with boronate rearrangement, eliminating the need for organolithium reagents, cryogenic conditions, or complex setups. The available trifluoromethylarenes are employed as carbenoid precursors for the first time, expanding the scope of the Matteson reaction. In collaboration with Prof. Yangjian Quan’s group at HKUST, comprehensive mechanistic studies were conducted to support this work, including the identification of key reaction intermediates, DFT calculations, and electrochemical analysis.
This work marks the first application of electrochemistry in the Matteson reaction, offering a proof-of-concept solution to overcome the limitations of traditional methods. It modernizes the reaction and provides valuable insights for further advancements in organoboron chemistry and organic synthesis.
The co-first authors of this work are postgraduate student Mr. Tsoh Lam Cheung and postdoctoral researcher Dr. Yujun Li from the Lyu group.
Details: Electrochemical defluorinative Matteson-type homologation