Sustainable Production of Reduced Phosphorus Compounds: Mechanochemical Hydride Phosphorylation Using Condensed Phosphates as a Route to Phosphite

Phosphorus removal and recovery technologies have been implemented to tackle the anthropogenic eutrophication caused by phosphate runoff into waterways. In pursuit of a better utilization of the phosphates recovered from waste water treatment, we herein report that condensed phosphates can be employed to phosphorylate hydride reagents under solvent-free mechanochemical conditions to furnish phosphite (HPO3)2−, a versatile chemical with phosphorus in the +3 oxidation state. Hydride phosphorylation, as a two-electron one-proton reduction of a main group element oxide, constitutes a direct parallel with CO2 reduction to formate. Using potassium hydride as the hydride source, sodium trimetaphosphate (Na3P3O9 ), triphosphate (Na5P3O10), and pyrophosphate (Na4P2O7) engendered phosphite in 44, 58, and 44% yields based on total P content, respectively, under their optimal conditions. Formation of overreduced products including hypophosphite (H2PO2−) was identified as a competing process, and mechanistic investigation revealed that hydride attack on in situ generated phosphorylated phosphite species is a potent pathway for overreduction. The phosphite generated from our method could be easily isolated in the form of barium phosphite, a useful intermediate for production of phosphorous acid. This method circumvents the need to pass through white phosphorus (P4) as a high energy intermediate and mitigates involvement of environmentally hazardous chemicals. A bioproduced polyphosphate from baker’s yeast was demonstrated to be a viable starting material for the production of phosphite. This example demonstrates the possibility of accessing reduced phosphorus compounds in a more sustainable manner, and more importantly, closing the modern phosphorus cycle.

The Aryne Phosphate Reaction

Condensed phosphates are a critically important class of molecules in biochemistry, with a myriad of derived structures being known. Moreover, non-natural analogues are important for various applications, such as single molecule real time DNA sequencing. Often, such analogues contain more than three phosphate units in their oligophosphate chain. Consequently, investigations into phosphate reactivity enabling new ways of phosphate functionalization and oligophosphorylation are an essential endeavour in the field. Here, we scrutinize the potential of phosphates to act as arynophiles, paving the way for follow-up oligophosphorylation reactions. The aryne phosphate reaction is a powerful tool to – depending on the perspective – (oligo)phosphorylate arenes or arylate (oligo-cyclo)phosphates. Based on Kobayashi-type o-silylaryltriflates, the aryne phosphate reaction enables rapid entry into a broad spectrum of arylated products, like monophosphates, diphosphates, phosphodiesters and polyphosphates. The synthetic potential of these new transformations is demonstrated by efficient syntheses of nucleotide analogues and an unprecedented one-flask octaphosphorylation.

The chemistry of branched condensed phosphates

Condensed phosphates may exist as linear, cyclic or branched structures. Due to their important role in nature, linear polyphosphates have been well studied. In contrast, branched phosphates (ultraphosphates) remain largely uncharacterised, because they were already described in 1950 as exceedingly unstable in the presence of water, epitomized in the antibranching-rule. This rule lacks experimental backup, since, to the best of our knowledge, no rational synthesis of defined ultraphosphates is known. Consequently, detailed studies of their chemical properties, reactivity and potential biological relevance remain elusive. Here, we introduce a general synthesis of monodisperse ultraphosphates. Hydrolysis half-lives up to days call the antibranching-rule into question. We provide evidence for the interaction of an enzyme with ultraphosphates and discover a rearrangement linearizing the branched structure. Moreover, ultraphosphate can phosphorylate nucleophiles such as amino acids and nucleosides with implications for prebiotic chemistry. Our results provide an entry point into the uncharted territory of branched condensed phosphates.

The Chemistry of Branched Condensed Phosphates

<p>Our manuscript explores the uncharted territory of the linear branched ultraphosphates by developing and combining synthesis, purification, analysis, and computational approaches. This group of condensed phosphates as true constitutional isomers of the linear polyphosphates was believed to be exceedingly unstable. This notion is proven wrong and we provide first evidence of their rich chemistry (rearrangements), biology (interaction with enzymes) and their potential in prebiotic phosphorylation chemistry. </p>

The Chemistry of Branched Condensed Phosphates

<p>Our manuscript explores the uncharted territory of the linear branched ultraphosphates by developing and combining synthesis, purification, analysis, and computational approaches. This group of condensed phosphates as true constitutional isomers of the linear polyphosphates was believed to be exceedingly unstable. This notion is proven wrong and we provide first evidence of their rich chemistry (rearrangements), biology (interaction with enzymes) and their potential in prebiotic phosphorylation chemistry. </p>

Safety assessment of condensed phosphate intake from fishery and processed marine food products in Korea with respect to gender, age, and region

Condensed phosphates are used as food additives, especially in marine products and meat, to improve food quality. The import and consumption of fishery and processed marine food products in Republic of Korea have reportedly increased by ~5 per cent annually. However, processed marine food products are often intentionally adulterated with excessive amounts of condensed phosphates to increase their weight. Excessive intake of condensed phosphates via consuming processed marine food products can lead to various adverse effects on human health due to anionic imbalance. Herein, we conducted a safety assessment of condensed phosphates in 14 types of fishery and processed marine food products in Korea for the first time. Subgroup analysis of various factors including gender, age, and region was also performed, and the risk level of exposure for each group was estimated. Safety assessments by age and gender indicated that infants were at the highest risk. In the regional safety assessment, Chungnam, the most inland region, showed the lowest risk. For both the general and the high-intake groups (95th percentile) in all classifications, the risk was lower (&lt;20 per cent) than the international standard, and the phosphorus content of the 14 types of processed marine products in Korea was confirmed to be safe for human consumption.