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. 2013 Jan 16;135(2):594-7.
doi: 10.1021/ja310980q. Epub 2013 Jan 8.

Diametric stereocontrol in dynamic catalytic reduction of racemic acyl phosphonates: divergence from α-keto ester congeners

Michael T Corbett  1 , Jeffrey S Johnson
Affiliations

Diametric stereocontrol in dynamic catalytic reduction of racemic acyl phosphonates: divergence from α-keto ester congeners

Michael T Corbett et al. J Am Chem Soc. .

Abstract

An unexpected dichotomy was observed in the Ru-catalyzed asymmetric transfer hydrogenation of acyl phosphonates: reduction proceeded from the opposite face relative to that observed in the analogous reduction of α-keto esters. The first highly selective catalytic hydrogenation of acyl phosphonates was utilized in the dynamic kinetic resolution of α-aryl acyl phosphonates, providing β-stereogenic α-hydroxy phosphonic acid derivatives.

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Figures

Figure 1
Figure 1
Reversal in enantiofacial selectivity.
Figure 2
Figure 2
Variables that potentially account for stereoselectivity inversion.
Scheme 1
Scheme 1
DKR-ATH of cyclic substrate 1q.
Scheme 2
Scheme 2
ATH of acyl phosphonates.
See this image and copyright information in PMC

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