[reaction: see text] The generality of catalytic, enantioselective alpha-additions of isocyanides to aldehydes has been demonstrated (Passerini-type reactions). The catalytic system of silicon tetrachloride and a chiral bisphosphoramide (R,R)-1b provided high yields and good to excellent enantioselectivities for the addition of tert-butyl isocyanide to a wide range of aldehydes (aromatic, heteroaromatic, olefinic, acetylenic, aliphatic). Aqueous workup afforded the alpha-hydroxy tert-butyl amides whereas a low-temperature methanol quench followed by basic workup afforded the alpha-hydroxy methyl esters. The reaction is also successful for other isocyanides, albeit with reduced enantioselectivity. Reaction conditions, particularly the rate of addition of the isocyanide was found to be crucial for good yields and high selectivities.