Electrochemical and photocatalytic generation of cis-olefin-bridged carbodication for umpolung [4+1] cycloaddition with primary amines or H2O

Electrochemical and photocatalytic generation of cis-olefin-bridged carbodication for umpolung [4+1] cycloaddition with primary amines or H2O | 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 Electrochemical and photocatalytic generation of cis-olefin-bridged carbodication for umpolung [4+1] cycloaddition with primary amines or H2O Tienan Jin, Hidenori Matsuyama, Kaisei Yokoyama, Takuma Sato, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6841083/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 02 Feb, 2026 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract Carbodications, bearing two positive charges on carbon atoms, are emerging as powerful superelectrophiles in organic synthesis. Traditionally formed through single-electron oxidation of overcrowded electron-rich alkenes or acid-mediated dehydration of diols, these species show high reactivity toward carbon-based nucleophiles. However, their reactivities with heteroatom nucleophiles like amines and water remain underexplored, largely due to difficulties in controlling oxidation and undesirable acid–base interactions. Here, we report for the first time that carbodication species generated under mild electrochemical or photocatalytic conditions display remarkable electrophilic reactivity toward primary amines and water. This enables a novel intermolecular umpolung [4+1] cycloaddition, proceeding via a cis-olefin-bridged dicationic intermediate, energetically favored over its trans-isomer, yielding a new class of thioxanthene-based dispirocycles with 2,5-dihydro-1H-pyrrole or 2,5-dihydrofuran central cores. Theoretical studies of electrochemical cycloaddition with aniline suggest that hydrogen bonding between aniline and the fluorine atom of the nBu₄PF₆ electrolyte stabilizes the transition state, promoting nucleophilic addition. Physical sciences/Chemistry/Organic chemistry/Synthetic chemistry methodology Scientific community and society/Energy and society Full Text Additional Declarations There is NO Competing Interest. Supplementary Files SIdication.pdf Supplementary Infromation Cite Share Download PDF Status: Published Journal Publication published 02 Feb, 2026 Read the published version in Nature Communications → 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. 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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-6841083","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":474952686,"identity":"5eb9e293-7c89-4bff-b54a-094e9acd47d2","order_by":0,"name":"Tienan 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