Characterization of Phosphoranes Obtained by the Spontaneous Carbonyl‐Catalyzed Phosphorylation of Monosaccharides and Polyols in Aqueous Media

• Published in: Chembiochem : a European journal of chemical biology Vol. 21; no. 4; pp. 473 - 476
• Main Authors: Perez‐Ramirez, Maria, Agyekum, Isaac, Otoo, Barnabas
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 17.02.2020
• Subjects: Acetals; activation; Adenosine; Alcohols; Aldehydes; Aqueous solutions; biophosphorylation; Carbonyl compounds; Carbonyls; Catalysis; Dehydration; Hydrolysis; Intermediates; Ketones; Mass spectroscopy; Monosaccharides; Monosaccharides - chemistry; Phosphates; Phosphates - chemistry; phosphoranes; Phosphoranes - chemical synthesis; Phosphorylation; Polymers - chemistry; Polyols; Radiolabelling; Reagents; Ribonucleic acid; RNA; Substrates; Sugar; Thermodynamics; Transesterification; Uridine; biophosphorylation; phosphoranes; monosaccharides; polyols; activation
• ISSN: 1439-4227; 1439-7633; 1439-7633
• DOI: 10.1002/cbic.201900328

Phosphorylation is a very important biochemical process in metabolism and biochemical marking. The mechanism for the biophosphorylation of substrates and the hydrolysis/transesterification of RNA has been suggested to proceed through phosphorane intermediates. Although the phosphorane intermediate/transition state has long been a subject of many theoretical models and studies, it has neither been isolated nor characterized, with most information derived from the hydrolysis and radiolabeling of cyclic phosphotriesters. We herein present the first report of the spontaneous phosphorylation of sugars and polyols in the absence of enzymes. That is, aldehydes and ketones combine with inorganic phosphates to form activated phosphates that phosphorylate alcohols without the requirement of any enzyme or additional activating agent. This phosphorylation is particularly favored in polyhydroxycarbonyls that can form internal cyclic acetals to give rise to the corresponding acetal phosphoranes. We have further characterized these phosphoranes and demonstrated their dehydration to the corresponding phosphates by using high‐resolution mass spectroscopy. The phosphorylation of adenosine and uridine to form the corresponding phosphoranes was also achieved. Rethink biophosphorylation: Inorganic phosphates are activated by water‐soluble aldehydes and ketones leading to the spontaneous phosphorylation of polyols to form phosphoranes. In the case of monosaccharides, the activation is achieved internally. The spontaneity of the reaction suggests that it is the first step in biophosphorylation.