It was found for the first time that cinchonine- and BINOL-derived multifunctional ligands bearing a silicon-based bulky group exhibited promising enantioselective control in the ruthenium-catalysed carbenoid N–H insertion reaction, in which the Ru–L26 system with multiple stereogenic centers was proved to be an enzyme-like catalyst because it exhibited a narrow substrate scope and size-sensitive discrimination in this reaction.