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Enantioselective synthesis of P-chiral tertiary phosphine oxides with an ethynyl group via Cu(i)-catalyzed azide–alkyne cycloaddition

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Abstract

We report the highly enantioselective synthesis of P-chiral tertiary phosphine oxides featuring an ethynyl group via Cu(I)-catalyzed azide–alkyne cycloaddition. Newly developed chiral pyridinebisoxazolines (PYBOX) bearing a bulky C4 shielding group play an important role in achieving excellent enantioselectivity while suppressing side bis-triazoles formation in desymmetrizing prochiral diethynylphosphine oxides. Notably, by tuning the size of the C4 shielding group, it is possible to achieve excellent remote enantiofacial control in desymmetrizing phosphole oxide-diynes with the prochiral P-center farther from the ethynyl group by four covalent bonds. Time-dependent enantioselectivity is observed for these desymmetric CuAAC reactions, suggesting a synergic combination of a desymmetrization and a kinetic resolution, and our ligands prove to be better than unmodified PYBOX in both steps. This finding contributes to a highly enantioselective kinetic resolution of racemic ethynylphosphine oxides. The resulting chiral ethynylphosphine oxides are versatile P-chiral synthons, which can undergo a number of diversifying reactions to enrich structural diversity.

Graphical abstract: Enantioselective synthesis of P-chiral tertiary phosphine oxides with an ethynyl group via Cu(i)-catalyzed azide–alkyne cycloaddition

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Publication details

The article was received on 01 Oct 2019, accepted on 05 Nov 2019 and first published on 06 Nov 2019


Article type: Edge Article
DOI: 10.1039/C9SC04938J
Chem. Sci., 2020, Advance Article
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    Enantioselective synthesis of P-chiral tertiary phosphine oxides with an ethynyl group via Cu(I)-catalyzed azide–alkyne cycloaddition

    R. Zhu, L. Chen, X. Hu, F. Zhou and J. Zhou, Chem. Sci., 2020, Advance Article , DOI: 10.1039/C9SC04938J

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