Enantio‐ and Diastereoselective Rh(I)‐Catalyzed Defluorinative Arylation of Pentafluoroethyl Alkenes to Access Fluoroalkenes Featuring a Unique F‐ and <scp> CF ₃ </scp> ‐Substituted <i>sp</i> ^<i>2</i> ‐Carbon ^†

Comprehensive Summary We herein describe an enantio‐ and diastereoselective rhodium(I)‐catalyzed defluorinative arylation of pentafluoroethyl alkenes with arylboronic acids. A new class of previously inaccessible functionalized fluoroalkenes featuring a sp 2 ‐carbon connected to F and CF 3 can be synthesized. Using both 1,1‐ and 1,2‐disubstituted alkene substrates, tetra‐ and trisubstituted fluoroalkene products are obtained in excellent Z / E selectivities with well‐defined alkene geometry. These fluoroalkenes are potential synthons for accessing chiral compounds containing a stereogenic centre with F and CF 3 group.