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Updated: Jun 2, 2025

Synthesis of Information-bearing Peptoids and their Sequence-directed Dynamic Covalent Self-assembly
Published on: February 6, 2020
Asymmetric Amplification in Oxypalladation/Malononitrile Addition Cascade Enabled by Heterochiral-Assembly of
Xiao-Wen Zhang1, Qi-Yang Li1, Wei Yan1
1Hubei Research Center of Fundamental Science-Chemistry, Engineering Research Center of Organosilicon Compounds & Materials, Hubei Key Lab on Organic and Polymeric Optoelectronic Materials, and College of Chemistry and Molecular Sciences, Wuhan University, 299 Bayi Rd, Wuhan 430072, China.
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).
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