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Despite extensive research on well\u2010characterized exhaustively phosphorylated PP\u2010InsPs, such as 5\u2010PP\u2010InsP\n                    <jats:sub>5<\/jats:sub>\n                    (5\u2010InsP\n                    <jats:sub>7<\/jats:sub>\n                    ) and 1,5\u2010(PP)\n                    <jats:sub>2<\/jats:sub>\n                    \u2010InsP\n                    <jats:sub>4<\/jats:sub>\n                    (1,5\u2010InsP\n                    <jats:sub>8<\/jats:sub>\n                    ), the functional relevance of less abundant not fully phosphorylated isomers, remains largely unknown. In this study, we synthesized all unsymmetric 5\u2010PP\u2010InsP\n                    <jats:sub>4<\/jats:sub>\n                    isomers in enantiopure form and assigned their structures using\n                    <jats:sup>31<\/jats:sup>\n                    P\u2010NMR analysis in combination with a chiral solvating agent. Additionally, we developed\n                    <jats:sup>18<\/jats:sup>\n                    O\u2010labeled PP\u2010InsP\n                    <jats:sub>4<\/jats:sub>\n                    standards for mass spectrometry in combination with capillary electrophoresis (CE\u2010MS), enabling the assignment of PP\u2010InsP\n                    <jats:sub>4<\/jats:sub>\n                    in\n                    <jats:italic>Arabidopsis thaliana<\/jats:italic>\n                    under phosphate starvation. Our findings show that the previously detected, phosphate starvation\u2010induced root\u2010specific PP\u2010InsP\n                    <jats:sub>4<\/jats:sub>\n                    isomer does not match any 5\u2010PP\u2010InsP\n                    <jats:sub>4<\/jats:sub>\n                    isomer, contrary to previous suggestions, thus indicating an alternative phosphorylation pattern. Enzyme assays further demonstrate that\n                    <jats:italic>Arabidopsis<\/jats:italic>\n                    ITPK1 selectively phosphorylates [6\u2010OH]\u2010InsP\n                    <jats:sub>5<\/jats:sub>\n                    and [3\u2010OH]\u2010InsP\n                    <jats:sub>5<\/jats:sub>\n                    at the 5\u2010position, while other InsP\n                    <jats:sub>5<\/jats:sub>\n                    isomers remain unchanged. This suggests that an unidentified enzymatic activity is involved in the formation of the elusive root PP\u2010InsP\n                    <jats:sub>4<\/jats:sub>\n                    species. Our study provides a comprehensive framework for the synthesis, analysis, and functional investigation of PP\u2010InsP\n                    <jats:sub>4<\/jats:sub>\n                    , providing an entry point for future studies on their biochemical activity and their physiological roles.\n                  <\/jats:p>","DOI":"10.1002\/anie.202507058","type":"journal-article","created":{"date-parts":[[2025,7,1]],"date-time":"2025-07-01T09:34:18Z","timestamp":1751362458000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Expanding the Inositol Pyrophosphate Toolbox: Stereoselective Synthesis and Application of PP\u2010InsP\n                    <sub>4<\/sub>\n                    Isomers in Plant Signaling"],"prefix":"10.1002","volume":"64","author":[{"given":"Kevin","family":"Ritter","sequence":"first","affiliation":[{"name":"Faculty of Chemistry and Pharmacy, Institute of Organic Chemistry, and CIBSS\u2010Centre for Integrative Biological Signaling Studies Albert\u2010Ludwigs University Freiburg Freiburg 79104 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anne\u2010Sophie C.","family":"Braun","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Pharmacy, Institute of Organic Chemistry, and CIBSS\u2010Centre for Integrative Biological Signaling Studies Albert\u2010Ludwigs University Freiburg Freiburg 79104 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guizhen","family":"Liu","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Pharmacy, Institute of Organic Chemistry, and CIBSS\u2010Centre for Integrative Biological Signaling Studies Albert\u2010Ludwigs University Freiburg Freiburg 79104 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mengsi","family":"Lu","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Pharmacy, Institute of Organic Chemistry, and 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