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Cobalt-Catalyzed Regio- and Enantioselective Allylic Alkylation of Malononitriles

Samir Ghorai, Sajid Ur Rehman, Wenbin Xu, Wenyu Huang, Changkun Li

2020Organic Letters60 citationsDOI

Abstract

Cobalt-catalyzed highly branched- and enantioselective allylic alkylation of malononitriles has been developed. Chiral γ,δ-unsaturated malononitriles could be synthesized with >20:1 branched/linear regioselectivity and up to 99% enantiomeric excess from easily accessible racemic allylic carbonates under mild reaction conditions. The electron-rich and sterically less hindered bisoxazolinephosphine ligand is essential to realize the high reactivity in the carbon-carbon bond formation process.

Topics & Concepts

ChemistryRegioselectivityEnantioselective synthesisTsuji–Trost reactionAllylic rearrangementReactivity (psychology)Steric effectsCobaltCatalysisAlkylationLigand (biochemistry)EnantiomerOrganic chemistryMedicinal chemistryCombinatorial chemistryMedicinePathologyAlternative medicineBiochemistryReceptorAsymmetric Synthesis and CatalysisAsymmetric Hydrogenation and CatalysisSynthetic Organic Chemistry Methods