Collaboration by Professor Ken Houk’s group and Chinese researchers leads to breakthrough in the field of metal difluorocarbene chemistry.
In their paper, published in the September 23, 2019 issue of the prestigious journal Nature Chemistry, the team reveals how to generate palladium difluorcarbenes and make them act either as electron-rich (nucleophilic) species or electron-deficient (electrophilic) reactants.
Houk and two-year Visiting Scholar Dr. Xiaosong Xue, an Associate Professor at Nankai University, collaborated with Professor Xingang Zhang’s experimental group at the Shanghai Institute of Organic Chemistry (SIOC) to make this breakthrough.
After several decades of investigation, the Zhang group discovered how to tune electrophilicity and nucleophilicity of the palladium difluorocarbene species, and the Houk-Xue calculations show why this works. Fluorinated aromatics are common in many effective pharmaceuticals, and such methods are highly valued for their synthesis. Professors Houk and Xue are pictured right during Houk’s recent visit to Nankai University.
The diagram below shows the 4 products, 4-7, that can be made, and appropriate control of Pd oxidation state, reagents or ligands allowed selective formation of any of the 4 compounds, 4, 5, 6, or 7!
Xue and Houk are also coauthors of a Nature paper about metal-free CH functionalization to be published in early October 2019.
The image that Houk and Xue submitted to Nature Chemistry as a possible cover.
Houk, UCLA’s Saul Winstein Professor of Organic Chemistry, has pioneered the use of computer calculations and simulations to study organic chemistry and to predict chemical reactivity that will have important applications in industry and in therapies for fighting disease. To learn more about Houk’s research, visit his group’s website.
