o-Benzenedisulfonimide (OBS) has efficiently catalysed the one-pot three-component reaction of ketones and aromatic amines with trimethylsilyl cianide (TMSCN) giving the corresponding α-amino nitriles in excellent yields (23 examples; average yield 85%). Reaction conditions were very simple, green and efficient. Theoretical calculations have allowed us to explain the mechanism of this reaction which has been found to take place in two phases; the first consists of the nucleophylic addition of the aniline to the ketone and the subsequent dehydration to an imine; the second one consists of the formal addition of CN- to the protonated imine. OBS acts in all steps of this mechanism. Without an acid catalyst, the reaction mechanism is more simple but barriers are sensibly higher. A chiral derivative of OBS was also used and gave fairly good results.

o-Benzenedisulfonimide and its chiral derivatives as Brønsted acid catalyst for one-pot three-component Strecker reaction. Synthetic and mechanistic aspects.

BARBERO, Margherita;CADAMURO, Silvano;DUGHERA, Stefano;GHIGO, Giovanni
2012-01-01

Abstract

o-Benzenedisulfonimide (OBS) has efficiently catalysed the one-pot three-component reaction of ketones and aromatic amines with trimethylsilyl cianide (TMSCN) giving the corresponding α-amino nitriles in excellent yields (23 examples; average yield 85%). Reaction conditions were very simple, green and efficient. Theoretical calculations have allowed us to explain the mechanism of this reaction which has been found to take place in two phases; the first consists of the nucleophylic addition of the aniline to the ketone and the subsequent dehydration to an imine; the second one consists of the formal addition of CN- to the protonated imine. OBS acts in all steps of this mechanism. Without an acid catalyst, the reaction mechanism is more simple but barriers are sensibly higher. A chiral derivative of OBS was also used and gave fairly good results.
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http://pubs.rsc.org/en/Content/ArticleLanding/2012/OB/C2OB25584G
Brønsted Acids. Sulfonimides. Density functional calculations. Green Chemistry. Strecker reaction.
Margherita Barbero; Silvano Cadamuro; Stefano Dughera; Giovanni Ghigo
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/100933
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