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Herein, we report a steric hindrance\u2013mediated strategy that achieves switchable\n                    <jats:italic>Z<\/jats:italic>\n                    \/\n                    <jats:italic>E<\/jats:italic>\n                    selectivity via rational design of a metal\u2013organic\u2010functionalized phosphovanadomolybdate [PMo\n                    <jats:sub>8<\/jats:sub>\n                    V\n                    <jats:sub>4<\/jats:sub>\n                    O\n                    <jats:sub>40<\/jats:sub>\n                    (VO)\n                    <jats:sub>2<\/jats:sub>\n                    ][(VO)(IM)\n                    <jats:sub>4<\/jats:sub>\n                    ]\n                    <jats:sub>3<\/jats:sub>\n                    \u00b75.5H\n                    <jats:sub>2<\/jats:sub>\n                    O (IM\u00a0=\u00a01\u2010methylimidazole), which features a highly congested steric environment. Steric repulsion between the cluster framework and substrate enables highly\n                    <jats:italic>Z<\/jats:italic>\n                    \u2010selective hydrophosphorylation, affording\n                    <jats:italic>\u03b2<\/jats:italic>\n                    \u2010(\n                    <jats:italic>Z<\/jats:italic>\n                    )\u2010alkenylphosphine oxides in up to 81% yield with\n                    <jats:italic>Z<\/jats:italic>\n                    \/\n                    <jats:italic>E<\/jats:italic>\n                    ratio of 21:1. Incorporation of AgOAc as a stereochemical modulator switches the pathway to afford\n                    <jats:italic>\u03b2<\/jats:italic>\n                    \u2010(\n                    <jats:italic>E<\/jats:italic>\n                    )\u2010products in up to 80% yield with\n                    <jats:italic>E<\/jats:italic>\n                    \/\n                    <jats:italic>Z<\/jats:italic>\n                    ratios up to 15:1. This heterogeneous catalytic system exhibits broad substrate tolerance, accommodating a diverse range of terminal alkynes with excellent chemo\u2010 and regioselectivity, including in the functionalization of complex pharmaceuticals, agrochemicals, and natural products, and gram\u2010scale reactions with pharmaceutical substrates were achieved in this catalytic system. These findings not only provide practical solutions for stereodivergent hydrophosphorylation but also offer fundamental insights into steric control in transition metal\u2013catalyzed transformations.\n                  <\/jats:p>","DOI":"10.1002\/anie.8728083","type":"journal-article","created":{"date-parts":[[2026,7,30]],"date-time":"2026-07-30T15:56:32Z","timestamp":1785426992000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Sterically Engineered Mo\u2500V Cluster Catalyst for Switchable\n                    <i>Z<\/i>\n                    \/\n                    <i>E<\/i>\n                    \u2010Selective Alkyne Hydrophosphorylation"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0015-5278","authenticated-orcid":false,"given":"Yu\u2010Feng","family":"Liu","sequence":"first","affiliation":[{"name":"Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation Jiangxi Province Key Laboratory of Functional Organic Polymers East China University of Technology  Nanchang Jiangxi China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bao\u2010Kuan","family":"Chen","sequence":"additional","affiliation":[{"name":"School of Petrochemical Engineering Liaoning Petrochemical University  Fushun Liaoning China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4891-2290","authenticated-orcid":false,"given":"Guo\u2010Ping","family":"Yang","sequence":"additional","affiliation":[{"name":"Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation Jiangxi Province Key Laboratory of Functional Organic Polymers East China University of Technology  Nanchang Jiangxi China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3116-756X","authenticated-orcid":false,"given":"Zhi\u2010Ming","family":"Zhang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Crystal Materials Institute for New Energy Materials and Low Carbon Technologies School of Materials Science and Engineering Tianjin University of Technology  Tianjin 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