Abstract
An enantioselective oxypalladation/malononitrile addition cascade reaction of alkyne-tethered malononitriles was reported to synthesize enaminones bearing an all-carbon quaternary center. Using Pd(TFA)2/Pyox as a precatalyst, an array of enaminone products were obtained in moderate overall yields, with excellent er (93.5:6.5-99.5:0.5) in solution phase and nearly racemic in solid phase. The usage of 3,5-dinitrobenzoic acid as the nucleophile was proven to be crucial to this significant chiral amplification due to a heterochiral self-assembly of the products through an intermolecular multiple π-π stacking interaction. A strong positive nonlinear effect (NLE) was observed in solution phase, which was further highlighted by the access to an enantiopure enaminone (99.5:0.5 er) even using a partially enantiopure catalyst (54:46 er).
Published Version
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