Asymmetric Synthesis of P-Stereogenic Compounds via Thulium(III)-Catalyzed Desymmetrization of Dialkynylphosphine Oxides
ACS Catalysis2019Vol. 9(6), pp. 4834–4840
Citations Over TimeTop 10% of 2019 papers
Abstract
A chiral thulium(III)-catalyzed sulfur-conjugation addition reaction of dialkynylphosphine oxides to construct P-stereogenic centers has been developed. Dialkynylphosphine oxides bearing aryl, alkyl, alkenyl substitution at the alkyne terminus position were tolerated under the reaction conditions. The corresponding P,S-containing compounds were obtained in moderate to good yields (up to 92% yield) with high Z/E ratios and enantioselectivities (up to >95/5 Z/E and 97% ee), which could be transformed into versatile optically active phosphine oxide derivatives. X-ray single crystal structures of chiral N,N′-dioxides with rare-earth metal triflates revealed how the metal center and ligand structure affect the enantioselectivity.
Related Papers
- → Enantioselective Formation of Cyano‐Bearing All‐Carbon Quaternary Stereocenters: Desymmetrization by Copper‐Catalyzed N‐Arylation(2014)48 cited
- → Enantioselective Formation of Cyano‐Bearing All‐Carbon Quaternary Stereocenters: Desymmetrization by Copper‐Catalyzed N‐Arylation(2014)13 cited
- → Asymmetric Desymmetrization: Simultaneous Stereocontrol of Multi-chiral Centers.(2002)24 cited
- → Direct construction of d3-methylated all-carbon quaternary stereocenters through carbene-catalyzed desymmetrization(2023)2 cited
- → Trost Desymmetrization(2010)