Hydrogen-Bonding Cyclodiphosphazane Organocatalysts in Enantioselective Michael Additions

Dedication

Dedicated to Prof. Dr. Paul Knochel on the occasion of his 70th birthday.

Abstract

Chiral aryl-(1R,2R)-N,N-dimethyldiamino-cyclohexane (DMDACH)-substituted cyclodiphosphazanes are demonstrated to be efficient bifunctional hydrogen-bonding organocatalysts for the enantioselective Michael additions of 2-hydroxy-1,4-naphthoquinone (<90% ee), Meldrum’s acid (<55% ee), and kojic acid chloride (<80% ee) to β-nitrostyrene. The parent, unsubstituted phenyl-cyclodiphosphazane with PO functions shows superior enantioselectivity in most cases and even exceeds, with 55% ee, the enantioselectivity of Takemoto’s thiourea catalyst for the challenging Meldrum’s acid substrate (46% ee). For Michael additions of kojic acid chloride, the meta-CH₃-substituted cyclodiphosphazane with PS functions is the most enantioselective (< 80% ee) catalyst. This highlights the benefits of modular cyclodiphosphazane structures, which can be tailored for specific substrates.

Keywords

Asymmetric catalysis - Michael additions - Enols - Stereoselective synthesis - Phosphates - Hydrogen bonding - Cyclodiphosphazanes - Organocatalysis - Enantioselectivity - Hydroxyquinones - Meldrum’s acid - Kojic acid - Nitrostyrene

Publikationsverlauf

Eingereicht: 04. April 2025

Angenommen nach Revision: 15. Mai 2025

Artikel online veröffentlicht:
24. Juli 2025

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