Using a simple combination of tri-tert-butylphosphine and chiral borane generated in situ by the hydroboration of chiral diene with HB(C6F5)(2) as a frustrated Lewis pair catalyst, a highly enantioselective metal-free hydrogenation of silyl enol ethers was successfully realized to furnish a variety of optically active secondary alcohols in 93-99% yields with 88->99% ee's.