Selective Monophosphorylation of Aliphatic Diamines

Phosphorus, Sulfur, and Silicon and the Related Elements, 1995

Phosphorylation of amines, alcohols, and sulfoximines are accomplished using molecular iodine as a catalyst and H 2 O 2 as the sole oxidant under mild reaction conditions. This method provides an easy route for synthesizing a variety of phosphoramidates, phosphorus triesters and sulfoximine-derived phosphoramidates which are of biological importance. Phosphoramidates and phosphate esters are structural scaffolds that are present in a variety of biologically active molecules. 1 Apart from their presence in a variety of biologically active natural products, phosphoramidates are useful pharmaceuticals (e.g., anti-HIV pro-drugs, cancer therapeutics, etc.) 2 and used as ligands 3a in asymmetric synthesis and hydroaminoalkylation catalysis, 3b as flame retardants, 3c and for efficient ionization in mass spectro-metric applications. 3d Phosphorylation of amines provides an excellent protocol for the protection of amines, which are stable to Lewis acids and can be cleaved by dilute mineral acids. 4 Similarly, phosphate esters are an integral part of a variety of naturally occurring molecules, such as nucleic acids, proteins, carbohydrates, steroids, and coen-zymes, and are used as pro-drugs. 5 Phosphate esters such as benzyl phosphates are employed as coupling partners in SuzukiÀMiyaura cross-coupling reactions. 6 The utility of the phosphoryl group as a directing group for CÀC bond-forming reactions has been well established. 7 For these reasons, the syntheses of phosphoramidate/phosphate es-ters are of great importance. The conventional methods for (1) (a) Phillips, D. R.; Uramoto, M.; Isono, K.; McCloskey, J. A.

Russian Chemical Bulletin, 1997

The reaction of aryl and aralkyl aldoximes with hypophosphorous acid resulted in aminophosphinic acids, which were oxidized into the corresponding aminophosphonic acids.

Phosphorus, Sulfur, and Silicon and the Related Elements, 2009

The synthesis of , -dehydro--aminophosphonic and , -dehydro--aminophosphinic acid derivatives is discussed. The most important synthetic pathways to the above-mentioned compounds have been divided into four groups depending on the type of bond formed as the last one. The configuration at the C=C double bond can be established based on the specific coupling constants 3 JHP and 3 JCP for the appropriate Z-and E-stereoisomers. The application of , -dehydro--aminophosphonates and , -dehydro-aminophosphinates, particularly in the enantioselective catalytic hydrogenation, is also discussed.

Tetrahedron, 2001

ÐThe synthesis of two new series of functional phosphines oxides is described: analogs of glyphosate [a-aminomethylbis-(hydroxymethyl)phosphine oxide] and bisphosphonic acids [bis(hydroxymethyl)phosphoryl methylphosphonic acid] substituting the phosphonic group [±P(O)(OH) 2 ] by the bis(hydroxymethyl)phosphoryl group [±P(O)(CH 2 OH) 2 ], have been synthesized in good yields, using the bis(benzyloxymethyl)chloromethyl phosphine oxide as a common precursor. The further purpose of this work is to evaluate the biological interest of the bis(hydroxymethyl)phosphoryl group in comparison to the phosphonic group present in a wide range of biological molecules.

Russian Chemical Bulletin, 1999

Polyhedron, 1988

The reactions of R2PPR2 (R = Me, Et, Ph) and (MeP)5 with Me3_,As(NMe2), (n = 1, 2, 3) and of Me,PPMe, with Me2AsNR; (R' = Et, PI", and Pfi were investigated as a function of time at room temperature using 'H and 3'P NMR spectroscopy. For the diphosphine/Me,AsNR; reactions, the NMR spectral data suggest a reaction pathway involving the initial formation of R2PAsMe2 and the respective acyclic dialkylaminophosphine, R,PNR;. The P-As intermediate then symmetrizes to R2PPR2 and Me2AsAsMe2, the parent aminoarsine is completely consumed, and additional R2PNR2 is formed. The relative rate of aminophosphine production is dependent upon the nature of the substituent on the phosphorus and nitrogen atoms. For systems involving MeAs(NMez)2 and As(NMe2), as reactants, the intermediates could not be characterized, but the products were the expected aminophosphine and (MeAs), or elemental arsenic, respectively. (MeP)5 reacts to give MeP(NMe2)2 and the expected As-As bonded species. A comparison of the reactivity of these systems with analogous diarsine/aminoarsine systems is discussed. The results of the NMR study were utilized in designing a convenient, high yield, synthetic route to acyclic aminophosphines.

Synthesis

A simple, reproducible, and efficient preparation of new heterocyclic a-aminomethyl-H-phosphinic acids is reported. The synthetic protocol is based on the application of bis(trimethylsilyl) phosphonite, as an efficient phosphorous nucleophile, in the reac-tion with the corresponding heterocyclic imines. Subsequent meth-anolysis of the addition intermediates leads to the expected heterocyclic a-aminomethyl-H-phosphinic acids in fair to good yields. Additionally, acidic hydrolysis of benzhydrylamino deriva-tives allows the efficient preparation of free a-aminomethyl-H-phosphinic acids in good yields and high purity after simple crystal-lization. a-Aminoalkyl-H-phosphinic acids, as isosters of the natu-ral a-aminoalkylcarboxylic acids, and short peptides in-corporating this unit (i.e., phosphinic acid peptides) represent a very convenient mimic of a substrate in the transition state of hydrolytic enzymes and, therefore, they are considered as excellent enzyme inhibitors. 1 The effi-cie...

ChemInform, 2010