Functionalization of λ5-Phosphinines via Metalation Strategies – A New Route towards Fluorescent 3D-Aromatics

Functionalization of λ5-Phosphinines via Metalation Strategies – A New Route towards Fluorescent 3D-Aromatics | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Functionalization of λ5-Phosphinines via Metalation Strategies – A New Route towards Fluorescent 3D-Aromatics Dorian Didier, Flavie Rambaud, Bertrand Takam Fotie, Robert Naumann, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6874005/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 22 Dec, 2025 Read the published version in Communications Chemistry → Version 1 posted You are reading this latest preprint version Abstract We present herein the straightforward functionalization of l 5 -phosphinine derivatives using organometallic strategies. Halogen-zinc and -magnesium exchanges were successfully performed employing Et 2 Zn·2O amyl or i -PrMgCl·LiCl species under smooth reaction conditions. Such method allowed access to a wide range of sophisticated architectures, photophysical studies of which demonstrated interesting fluorescence properties. With the possibility of using such fluorescence in biomarking, l 5 -phosphinines were grafted on a few glycosides, nucleosides and pharmaceutically relevant moieties. The concept of “escaping the flatland” that refers to moving beyond simple, planar (two-dimensional) structures allows to explore the rich possibilities of three-dimensional molecular architectures.[ 1 ] Many organic compounds containing aromatic rings and conjugated systems are depicted as flat, which can limit their properties and interactions due to a restrained variety of exit vectors (orientation of substituents). However, introducing sp³-hybridized atoms, and non-planar ring systems allows chemists to access greater molecular complexity, which often leads to improved biological activity, selectivity, and physicochemical properties in drug design.[ 2 ] In this regard, we have developed methodologies towards the functionalization of four-membered molecular building blocks such as cyclobutanes[ 3 ] and azetidines,[ 4 ] strained, three-dimensional sp 3 -rich scaffolds that could be used as 3D-surrogates for classical aromatic structures such as phenyl- or pyridyl-moieties. Physical sciences/Chemistry/Organic chemistry/Synthetic chemistry methodology Physical sciences/Chemistry/Photochemistry/Single-molecule fluorescence Full Text Additional Declarations There is NO Competing Interest. Supplementary Files SuppInfoPhosphininesFlavie19052025.pdf Supporting Information Cite Share Download PDF Status: Published Journal Publication published 22 Dec, 2025 Read the published version in Communications Chemistry → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6874005","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":471944183,"identity":"a330e408-813b-4b87-87e8-82af79dbe55a","order_by":0,"name":"Dorian 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Halogen-zinc and -magnesium exchanges were successfully performed employing Et\u003csub\u003e2\u003c/sub\u003eZn\u0026middot;2O\u003cem\u003eamyl\u003c/em\u003e or \u003cem\u003ei\u003c/em\u003e-PrMgCl\u0026middot;LiCl species under smooth reaction conditions. Such method allowed access to a wide range of sophisticated architectures, photophysical studies of which demonstrated interesting fluorescence properties. With the possibility of using such fluorescence in biomarking, l\u003csup\u003e5\u003c/sup\u003e-phosphinines were grafted on a few glycosides, nucleosides and pharmaceutically relevant moieties.\u003c/p\u003e \u003cp\u003eThe concept of \u003cem\u003e\u0026ldquo;escaping the flatland\u0026rdquo;\u003c/em\u003e that refers to moving beyond simple, planar (two-dimensional) structures allows to explore the rich possibilities of three-dimensional molecular architectures.[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e] Many organic compounds containing aromatic rings and conjugated systems are depicted as flat, which can limit their properties and interactions due to a restrained variety of exit vectors (orientation of substituents). 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