Mild and general alumina-promoted hydrolysis conditions for converting α-iminonitriles into carboxamides have been developed. In combination with the oxidative three-component Strecker reaction, the one-pot direct amidation of aldehydes and alcohols is reported. Subsequently, an Yb(OTf)(3)-catalyzed Michael addition of thiols to α,β-unsaturated α-iminonitriles is reported for the synthesis of β-mercapto-α-iminonitriles. The successful integration of an oxidative Strecker reaction, thio-Michael addition, and neutral-alumina-promoted hydrolysis of β-mercapto-α-iminonitriles into a three-component one-pot process allowed us to develop the direct conversion of amines, aldehydes, and thiols into β-mercaptoamides. All of these procedures were applicable to aromatic and aliphatic amines and aldehydes.

Oxidative three-component reaction of aldehydes, amines, and TMSCN in a biphasic solvent system (toluene/H 2 O) containing Oxone, tetra-n-butylammonium bromide (TBAB) and sodium bicarbonate afforded α-iminonitriles in good to excellent yields. This oxidative Strecker reaction was applicable to a wide range of aldehydes and amines, aromatic or aliphatic, of different electronic and steric properties. Substituted 1-aza-2-cyano-1,3-dienes were also accessible using α,β-unsaturated aldehydes as inputs.

Synthesis of Iminonitriles by Oxone/TBAB-Mediated One-Pot Oxidative Three--Component Strecker Reaction. -The optimized conditions render possible the preparation of a broad spectrum of title compounds as building blocks for different substance classes. -(GUALTIEROTTI, J.-B.; SCHUMACHER, X.; WANG, Q.; ZHU*, J.; Synthesis 45 (2013) 10, 1380-1386, http://dx.doi.org/10.1055/s-0033-1316908 ; Inst. Chim. Sci. Eng., Ec. Polytech. Fed. Lausanne, CH-1015 Lausanne, Switz.; Eng.) -Mais 36-073

Microwave‐assisted amidation of aldehydes with amines is not applicable to aromatic aldehydes because products decompose under conditions used.