Asymmetric Amplification in Oxypalladation/Malononitrile Addition Cascade Enabled by Heterochiral-Assembly of Products

• DOI: 10.1021/acs.orglett.4c04591
• Publication Date: 2025-01-15T19:18:36Z
• Authors: Xiao-Wen Zhang; Qi-Yang Li; Wei Yan; Xu-Dong Hu; Wen-Bo Liu

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, array enaminone products were obtained in moderate overall yields, with excellent er (93.5:6.5-99.5:0.5) solution phase and nearly racemic solid phase. The usage 3,5-dinitrobenzoic acid the nucleophile proven be crucial this significant chiral amplification due heterochiral self-assembly through intermolecular multiple π-π stacking interaction. A strong positive nonlinear effect (NLE) observed phase, which further highlighted by access enantiopure (99.5:0.5 er) even using partially catalyst (54:46 er).