The first catalytic, asymmetric α-additions of isocyanides.: Lewis-base-catalyzed, enantioselective Passerini-type reactions

The first, catalytic, enantioselective α-additions of isocyanides to aldehydes have been demonstrated (Passerini-type reactions). The catalytic system of silicon tetrachloride and a chiral bisphosphoramide 5a provided high yields and good to excellent enantioselectivities for the addition of tert-butyl isocyanide to a wide range of aldehydes (aromatic, olefinic, acetylenic, aliphatic). Aqueous workup afforded the α-hydroxy tert-butyl amides, whereas methanolic quench followed by basic workup afforded the ∞-hydroxy methyl esters. Copyright © 2003 American Chemical Society.