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Chiral Magnesium(II) Binaphtholates as Cooperative Brønsted/Lewis Acid–Base Catalysts for the Highly Enantioselective Addition of Phosphorus Nucleophiles to α,β-Unsaturated Esters and Ketones


  • Financial support was partially provided by MEXT, KAKENHI (21200033, 24105512), the Program for Leading Graduate Schools: IGER Program in Green Natural Sciences (MEXT), and the Yazaki Memorial Foundation for Science and Technology. T.H. is grateful for a JSPS Research Fellowship for Young Scientists.


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A little cooperation goes a long way: The cooperative Brønsted/Lewis acid–base supramolecular catalysts formed in situ from simple chiral magnesium(II) binaphtholate aqua complexes promoted the highly enantioselective 1,4-hydrophosphinylation of α,β-unsaturated esters with diaryl phosphine oxides and 1,2-hydrophosphonylation of α,β-unsaturated ketones with dialkyl phosphites (see scheme).