Journal of the American Chemical Society p. 2994 - 3002 (2021)
Update date:2022-08-04
Topics: Asymmetric synthesis Enantiomer Column chromatography NMR spectroscopy Enantiomeric excess (ee) Recrystallization Catalytic reduction Recyclable Catalyst Substrate Scope Catalyst Loading Chiral HPLC Chiral Auxiliary Enantioselective Reduction Reaction Optimization Organocatalyst Prochiral Cyclic 1,3-diketones Solvent screening Turnover frequency (TOF) Turnover number (TON) Meso Compound
Qin, Xu-Long
Li, Ang
Han, Fu-She
The P-stereogenic phosphinamides are a structurally novel skeletal class which has not been investigated as chiral organocatalysts. However, chiral cyclic 3-hydroxy ketones are widely used as building blocks in the synthesis of natural products and bioactive compounds. However, general and practical methods for the synthesis of such chiral compounds remain underdeveloped. Herein, we demonstrate that the P-stereogenic phosphinamides are powerful organocatalysts for the desymmetric enantioselective reduction of cyclic 1,3-diketones, providing a useful method for the synthesis of chiral cyclic 3-hydroxy ketones. The protocol displays a broad substrate scope that is amenable to a series of cyclic 2,2-disubstituted five- and six-membered 1,3-diketones. The chiral cyclic 3-hydroxy ketone products bearing an all-carbon chiral quaternary center could be obtained with high enantioselectivities (up to 98% ee) and diastereoselectivities (up to 99:1 dr). Most importantly, the reactions could be practically performed on the gram scale and the catalysts could be reused without compromising the catalytic efficiency. Mechanistic studies revealed that an intermediate formed from P-stereogenic phosphinamide and catecholborane is the real catalytically active species. The results disclosed herein bode well for designing and developing other reactions using P-stereogenic phosphinamides as new organocatalysts.
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Doi:10.1039/b920606j
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