The Aryne Phosphate Reaction**

Abstract

Condensed phosphates are ac ritically important class of molecules in biochemistry.Non-natural analogues are important for various applications,s uch as single-molecule real-time DNAs equencing.O ften, 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,w es crutinizet he potential of phosphates to act as arynophiles,paving the way for follow-up oligophosphorylation reactions.The aryne phosphate reaction is ap owerful tool to-depending on the perspective-(oligo)phosphorylate arenes or arylate (oligo-cyclo)phosphates. Based on Kobayashi-type o-silylaryltriflates,t he aryne phosphate reaction enables rapid entry into ab road spectrum of arylated products,l ike monophosphates,d iphosphates,p hosphodiesters and polyphosphates.T he synthetic potential of these new transformations is demonstrated by efficient syntheses of nucleotide analogues and an unprecedented one-flask octaphosphorylation.

Pentaphosphorylation via the Anhydride of Dihydrogen Pentametaphosphate: Access to Nucleoside Hexa- and Heptaphosphates and Study of Their Interaction with Ribonuclease A

“…The acid form of pentametaphosphate ( 2 , [P 5 O 15 H 2 ] 3– ) appears not to have been reported previously, and even the reported syntheses of TBA + and NH 4 + salts of pentametaphosphate, [PO 3 ] 5 5− , suffer from tedious iterative purification procedures. , In contrast, the synthesis herein reported (Figure ) is selective and presents no purification or separation challenges. Dihydrogen pentametaphosphate 2 is facilely dehydrated back to 1 upon treatment with DCC.…”

Stabilized Molecular Diphosphorus Pentoxide, P2O5L2 (L = N-Donor Base), in the Synthesis of Condensed Phosphate–Organic Molecule Conjugates

“…To the best of our knowledge, the only previously published examples of cyclo -phosphonate-diphosphates were reported independently by our group and Jessen’s in 2019. , Many of these new compounds feature handles that enable further functionalization. Reported methods for the synthesis and modification of condensed phosphates are dominated by nucleophilic substitution reactions, − and so these compounds invite opportunities for exploring new orthogonal reactivity to expand structural diversity. − …”

Development of 3-triazenylaryne and its application to iterative aryne reactions via o-triazenylarylboronic acids

“…4 f In this context, this study develops 3-triazenylaryne as a novel aryne I , which can function as a platform for the generation of unexplored aryne species, that is, 3-alkynylarynes (Scheme 1b). 5…”