Tetrafluoroethylene Is Good For More Than Just Teflon

Tetrafluoroethylene (TFE) has long been used as an economical feedstock for making fluorinated polymers. Researchers have also used the fluorinated olefin as a starting material in organic synthesis, but the chemistry remains relatively underdeveloped. Two research teams are now reporting reactions that broaden the scope of TFE’s use as a reagent. In one case, a team led by Masato Ohashi and Sensuke Ogoshi of Osaka University, in Japan, has used TFE in nickel-catalyzed reactions with ethylene and aldehydes to make fluorinated aldehydes and ketones and with ethylene and other alkenes to make α-olefins with fluoroalkyl chains. The reactions proceed through an unprecedented five-membered “nickelacyclic” intermediate (J. Am. Chem. Soc. 2015, DOI: 10.1021/jacs.5b03587; Organometallics 2015, DOI: 10.1021/acs.organomet.5b00218). In a second case, Yusuke Takahira and Yoshitomi Morizawa of Asahi Glass, in Yokohama, Japan, have used TFE and other fluoroolefins in ruthenium carbene-catalyzed cross-metathesis reactions with enol ethers to make ether-functionalized fluorinated olefins (J. Am. Chem. Soc. 2015, DOI: 10.1021/jacs.5b03342). The Asahi researchers believe their method of combining inexpensive fluoroolefins with a hydrocarbon counterpart will enable easy synthesis of new fluorinated building blocks for polymeric materials and medicinal chemistry.