A General Strategy for the Synthesis of P‐Stereogenic Compounds

Abstract

A great leap forward toward the general synthesis of P-stereogenic compounds: Heating H3 PO2 with (-)-menthol and paraformaldehyde gives easily crystallized menthyl hydroxymethyl-H-phosphinate (1). From this product, virtually any P-stereogenic compound can be synthesized.

Manganese‐Mediated Intermolecular Arylation of H‐Phosphinates and Related Compounds

“…Finally, we recently disclosed a general solution to the preparation of P ‐stereogenic compounds based on RPO 2 H 2 (R=H, C) 18. Improving the recovery of HOCH 2 P(O)(OMen)H in the mother liquor was achieved through our Pd‐catalyzed cross‐coupling 15.…”

“…Deprotection and crystallization at room temperature then gave the highly enriched diastereoisomer 9 18. Diasteroisomer 10 18 was similarly arylated stereospecifically to afford known 11 ,18 thereby establishing the absolute configuration of the phosphorus atom and overall retention for the reaction. The higher yield (78 %) observed for 8 instead of 48 % for 11 is attributed to the larger scale in the preparation of 8 .…”

“…However, the entire process using the present methodology is ten times cheaper than the one using Pd‐catalyzed cross‐coupling 16. 18…”

Efficient Solid Acid Catalyst Containing Lewis and Brønsted Acid Sites for the Production of Furfurals

“…Furthermore, 1a and analogues have been obtained by the treatment of MenOPCl 2 with aryl Grignard reagents, followed by hydrolysis, resulting in yields of around 30 % of the diastereomerically pure product 5,6,10. Recently, Berger and Montchamp reported a multi‐step strategy to prepare 1a starting from hypophosphorous acid, paraformaldehyde, and (–)‐menthol 11. A straightforward and practical method suitable for the preparation of optically pure P–H species in satisfactory yield and on a ten‐gram scale has scarcely been developed.…”

Pd-catalyzed enantioselective C–H arylation of phosphinamides with boronic acids for the synthesis of P-stereogenic compounds

“…The most commonly used methods for the preparation of Pstereogenic molecules have mainly relied on resolution, [24][25][26] chiral-auxiliary-aided asymmetric synthesis, [27][28][29][30][31][32][33][34] and asymmetric lithiation-trapping reactions. [35][36][37][38] Other alternative methods include the NHC-catalyzed desymmetrization of bisphenolic phosphinates, 39 the metal-catalyzed asymmetric cross-coupling of phosphines or phosphine oxides, [40][41][42][43][44][45] hydrophosphination of olefins, 46 addition reactions of phosphorus nucleophiles, 47,48 and olefin metathesis of divinyl phosphinates.…”