α-Amido sulphones as useful intermediates in the preparation of C-chiral α-aminophosphonates and α-aminophosphonic acids.

α-Amido sulphones have been used as useful starting materials in the preparation of C-chiral α-aminophosphonates and α-aminophosphonic acids. The developed methodology is based on a one-pot, base-catalysed in situ generation of an imine intermediate followed by addition of a phosphorus nucleophile. The presented protocol is simple and effective and can be applied to a variety of structurally diverse α-amido sulphones and phosphorus nucleophiles, leading to the desired pure products after simple crystallization in very good yields. Importantly, the use of H-phosphonate bearing a chiral auxiliary allows the reaction to be performed with high diastereoselectivity (a single diastereoisomer is generated and isolated) and the possibility of precise control of the configuration at the newly generated C-chiral centre.

Asymmetric synthesis of organophosphorus compounds using H-P reagents derived from chiral alcohols.

Chiral organophosphorus compounds, especially those containing C-stereogenic carbons in the proximity of the phosphorus atom, are known for their unique properties and have found wide applications that span from medicinal chemistry to enantioselective catalysis. However, the synthesis of such chiral molecules, especially with the precise control of stereochemistry at chiral carbon atoms, still remains a very challenging task. This review summarizes recent advances in the highly stereoselective formation of C- and, in some cases, also P-stereogenic organophosphorus compounds. The presented synthesis strategy is based on the use of H-P reagents bearing TADDOL, BINOL or a menthol moiety attached to the phosphorus atom and serving as a chiral auxiliary. Reactions of such chiral H-P species with different partners, e.g., alkenes, alkynes, imines, and carbonyl compounds, leading to structurally diverse chiral organophosphorus compounds with up to five chiral centers are comprehensively discussed. In each case, the stereochemical outcome of the reaction is influenced by the presence of the chiral alcohol used; therefore, the content of this review is compiled into sections with respect to the type of chiral alcohol attached to the phosphorus atom in the H-P species applied.