An Efficient One-Pot Synthesis of New Polyfunctional Phosphorus Acid Amphiphiles

Abstract

The addition reaction between the P‐H bond of tetraoxyspirophosphoranes 1‐2 and long‐chain imines 3a‐h (decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and oleyl imines) occurs instantaneously at room temperature. It is diastereoselective, and quantitatively leads to the corresponding (α‐aminoalkyl)spirophosphoranes 4a‐h and 5e. The influence of the pentacoordinated phosphorus atom on the stereoselectivity of the Pudovik reaction might be attributed to the involvement of the rigid spirophosphoranide (PV) intermediate in the addition reaction. Selective and one‐pot hydrolysis of these P‐C bond spirophosphoranes readily proceeds either at room temperature in the presence of moist solvents to give the corresponding carboxyalkyl (α‐aminoalkyl)phosphonic acid monoesters 6a‐h and 7e, or the reaction may be carried out in the presence of 20% aqueous hydrochloric acid under reflux, to afford the free (α‐aminoalkyl)phosphonic acid amphiphiles 8a‐h in high yields. In contrast to their sodium salts, these single‐ and double‐chained free and monoester phosphonic acid amphiphiles exist as zwitterions and are not soluble in water.

Synthetic strategies of phosphonodepsipeptides

“…The addition reaction of the P-H bond of tetraoxyspirophosphoranes 199 to long-chain imines 200 of benzaldehyde, acetaldehyde, and dodecanal at room temperature generated the corresponding (α-aminoalkyl)spirophosphoranes 201 via the Pudovik reaction. The one-pot selective hydrolysis of the P-C bond of the spirophosphoranes 201 readily proceeded at room temperature in the presence of moist solvents to give the corresponding phosphonodepsipeptides 202 in high yields (Scheme 37) [56]. An asymmetric synthesis of this class of phosphonodepsipeptides was realized with enantiopure (S)-α-hydroxyisovaleric acid-derived spirophosphoranes as the phosphorus reagents [57].…”

Preparation and characterization of new hybrid organic/inorganic systems derived from calcium (α-aminoalkyl)-phosphonates and -phosphonocarboxylates

“…The synthesis and the characterization of phosphorus amphiphiles, (α-aminoalkyl)-phosphonocarboxylic 1 and -phosphonic 2 acids was already been described in a previous work [20]. The structure of carboxyisobutyl (α-aminoalkyl)-phosphonic acid monoesters 1 and (α-aminoalkyl)-phosphonic acids 2 are shown in Scheme 1.…”

“…In our team, we have synthesized in good yields a series of (α-aminoalkyl)-phosponocarboxylic and -phosphonic acids [20]. Their fields of application cover chemistry, medicine and agricultural science, due to their various complexing, biological and agrochemical properties [21][22][23].…”

Langmuir films of (α-amino) phosphorus amphiphiles on various ion-containing subphases

“…The phosphonocarboxylic and phosphonic acid amphiphiles were synthesized by the Pudovik reaction between a P-H bond spirophosphorane and long-chain aldimines, as described previously [11].…”

“…In our team, we have synthesized in good yields a series of (α-aminoalkyl)-phosponocarboxylic and -phosphonic acids [11] (see Scheme 1). Their fields of application cover chemistry, medicine, and agricultural science, due to their various complexing, biological, and agrochemical properties.…”