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A Phosphoramidite Analogue of Cyclotriphosphate Enables Iterative Polyphosphorylations
Authors:Jyoti Singh  Nicole Steck  Debaditya De  Alexandre Hofer  Alexander Ripp  Ilya Captain  Manfred Keller  Paul A. Wender  Rashna Bhandari  Henning J. Jessen
Abstract:An iterative polyphosphorylation approach is described, which is based on a phosphoramidite (P‐amidite) derived reagent (c‐PyPA) obtained from the cyclization of pyrophosphate with a reactive diisopropylaminodichlorophosphine. This type of reagent is unprecedented as it represents a reactive P‐amidite without protecting groups. The reagent proved to be stable in solution over several weeks. Its utility is described in the context of iterative monodirectional and bidirectional polyphosphorylations. The ensuing functionalized cyclotriphosphate can be opened with a variety of nucleophiles providing ready access to diverse functionalized polyphosphate chains of defined length with several tags, including both P‐N and P‐O labels. Their interaction with exo‐ and endopolyphosphatases is described.
Keywords:Cyclisches Phosphoramidit  Monodisperses polyP  Phosphor-Anhydride  Triphosphorylierung
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