Electrochemically programmable divergent semihydrogenation of enynes

Electrochemically programmable divergent semihydrogenation of enynes | 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 Electrochemically programmable divergent semihydrogenation of enynes Qiang Liu, Jie Yang, Songxuan Han This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9259550/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract The stereochemical configuration of diene motifs profoundly influences their physicochemical properties and biological activity. Despite this, general strategies for the divergent and stereodefined synthesis of isomeric dienes from common precursors remain scarce. Herein, we present an electrochemically programmable platform for the semihydrogenation of 1,3-enynes, achieving multidimensional selectivity control within a single reaction manifold to access diverse isomeric dienes. This platform selectively generates allenes via an electron transfer/proton transfer/hydrogen atom transfer (ET/PT/HAT) sequence in the absence of a catalyst, or 1,3-dienes upon introducing a cobalt catalyst that redirects the pathway through a Co(II)-H intermediate. Furthermore, fine modulation of the ligand architecture enables the selective formation of either Z- or E-configured dienes from the same starting material. This strategy marks a paradigm shift from conventional one-dimensional selectivity tuning to multidimensional selectivity programming, cooperatively leveraging the interplay of orthogonal parameters including the electrical regime, proton source, and catalyst. It thus offers a unified and tunable platform for accessing diverse, stereochemically defined diene libraries, crucial for advancements in medicinal chemistry and materials discovery. Physical sciences/Chemistry/Electrochemistry/Electrocatalysis Physical sciences/Chemistry/Organic chemistry/Synthetic chemistry methodology Full Text Additional Declarations There is NO Competing Interest. Supplementary Files CoBr2L7.cif CoBr2L7 CoBr2L7checkcif.pdf CoBr2L7checkcif SupplementaryInformation.pdf Supplementary Information Cite Share Download PDF Status: Under Review 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-9259550","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":622472720,"identity":"77da1fa0-c67d-462f-8403-8bdbf1ccdcba","order_by":0,"name":"Qiang 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Despite this, general strategies for the divergent and stereodefined synthesis of isomeric dienes from common precursors remain scarce. Herein, we present an electrochemically programmable platform for the semihydrogenation of 1,3-enynes, achieving multidimensional selectivity control within a single reaction manifold to access diverse isomeric dienes. This platform selectively generates allenes via an electron transfer/proton transfer/hydrogen atom transfer (ET/PT/HAT) sequence in the absence of a catalyst, or 1,3-dienes upon introducing a cobalt catalyst that redirects the pathway through a Co(II)-H intermediate. Furthermore, fine modulation of the ligand architecture enables the selective formation of either Z- or E-configured dienes from the same starting material. This strategy marks a paradigm shift from conventional one-dimensional selectivity tuning to multidimensional selectivity programming, cooperatively leveraging the interplay of orthogonal parameters including the electrical regime, proton source, and catalyst. 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