Litcius/Paper detail

P-stereogenic N-vinylphosphonamides enabled by asymmetric allylic substitution-isomerization

Xiulian Zhang, Xiaotian Qi, Ying-xiang Wu, Peng Liu, Ying He

2021Cell Reports Physical Science31 citationsDOIOpen Access PDF

Abstract

The catalytic and stereoselective synthesis of P-stereogenic compounds has drawn a lot of attention, since these compounds possess widespread applications in organic synthesis. Thus, novel strategies for the construction of new complex P-chiral molecules still need to be developed. Here, we report a highly enantioselective synthesis of P-stereogenic N-vinylphosphonamides using an asymmetric allylic substitution-isomerization (AASI) strategy. The efficient catalytic approach provides rapid access to a wide range of enantioenriched N-vinylphosphonamides in up to 85% yields and 99:1 enantiomeric ratio. Computational studies demonstrate that the P-stereogenic center induces more favorable π-π stacking interactions in N-vinylphosphonamides.

Topics & Concepts

StereocenterIsomerizationEnantioselective synthesisAllylic rearrangementStackingStereoselectivityEnantiomerStereochemistrySubstitution (logic)ChemistryCatalysisCombinatorial chemistryComputer scienceOrganic chemistryProgramming languageOrganophosphorus compounds synthesisAsymmetric Hydrogenation and CatalysisSynthetic Organic Chemistry Methods