<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Highly enantioselective metal‐free hydrogenation of silyl enol ethers is achieved by combining P(tBu)<sub>3</sub> with a chiral borane generated in situ by hydroboration of an axial‐chiral diene with HB(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub> as a frustrated Lewis pair catalyst.</p> </abstract>