Catalytic Asymmetric Synthesis of C-Chiral Phosphonates

Abstract

The current review is devoted to the achievements in the development of methods for the catalytic asymmetric synthesis of phosphonates containing a chiral center in the side chain. C-chiral phosphonates are widely represented among natural compounds with various biological activities as insecticides, herbicides, antibiotics, and bioregulators. Synthetic representatives of this class have found practical application as biologically active compounds. The review summarizes methods of asymmetric metal complex catalysis and organocatalysis as applied to such reactions as phospha-aldol reaction, two-component and three-component phospha-Mannich reaction, phospha-Michael reaction, as well as hydrogenation of unsaturated phosphonates and phosphine oxides, ketophosphonates, and iminophosphonates. Methods for the asymmetric hydride reduction of C=X phosphonates (X=O, S, NR) are also discussed in detail. The review presents updated literature reports, as well as original research by the author.

Stereoselective Syntheses of Organophosphorus Compounds

“…Three other stereoisomers are significantly inferior to it in activity. Many bioregulators and medicines have been developed based on aminophosphonic acids [38][39][40][41] (Figure 17).…”

Synthetic Methods for Azaheterocyclic Phosphonates and Their Biological Activity: An Update 2004–2024

“…Aminophosphonic acids attract a lot of attention because of their likeness to carboxylic acids and are therefore capable of mimicking the transition state of peptide cleavage reactions but as a stable molecule. Due this importance, they have been reviewed in the past. − Other works include phosphonates, phosphine oxides, other phosphine chalcogenides, and some phosphonamides, their scope is focused on a specific class of reactions, − or on a specific class of compounds. , The presence of the phosphorus atom in the design of drug molecules has been subject to its own review . focusing predominantly on the medicinal chemistry aspects and the range of receptors that can be affected.…”

Asymmetric construction of phosphono dihydropyranones from α-ketophosphonates enabled by Pd/chiral isothiourea relay catalysis

“…9 Despite considerable efforts having been devoted to this area, achieving precise control of stereochemistry from simple starting materials to afford structurally diverse chiral phosphonate compounds is still highly demanding. 10 The efficient synthesis of carbonyl compounds has garnered significant attention from researchers due to the accessible and straightforward procedures facilitated by Pd-catalyzed carbonylation reactions. 11 At the same time, asymmetric cascade reactions have emerged as an effective strategy for con-structing C-C or C-heteroatom bonds and are widely used for synthesizing useful organic molecules.…”

“…9 Despite considerable efforts having been devoted to this area, achieving precise control of stereochemistry from simple starting materials to afford structurally diverse chiral phosphonate compounds is still highly demanding. 10…”