The Aryne Phosphate Reaction. Issue 1 (22nd November 2021)

• Record Type: Journal Article
• Authors: Haas, Thomas M.; Wiesler, Stefan; Dürr‐Mayer, Tobias; Ripp, Alexander; Fouka, Paraskevi; Qiu, Danye; Jessen, Henning J.
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 1(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-11-22
• Subjects: aryne chemistry -- metaphosphates -- oligophosphorylation -- phosphorylation -- polyphosphates; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202113231
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Condensed phosphates are a critically important class of molecules in biochemistry. 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 essential. 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. Abstract : The ability of phosphates to act as efficient arynophiles is demonstrated. The resulting aryne phosphate reaction is a versatile tool for arene phosphorylation or phosphate arylation. A broad scope of variously arylated phosphate products is culminating in novel nucleotide analogues and a benchmarking octaphosphorylation.