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In particular, catalytic methods enabling flexible and stereodivergent synthesis of both\n                    <jats:italic>trans<\/jats:italic>\n                    \u2010selective and\n                    <jats:italic>cis<\/jats:italic>\n                    \u2010selective useful enol ethers are still underdeveloped. Herein, we report a manganese\u2010catalyzed, ligand\u2010controlled hydroalkoxylation of alkynylnitriles with alcohols under mild conditions. Through metal\u2013ligand cooperation, a range of (\n                    <jats:italic>Z<\/jats:italic>\n                    )\u2010 and (\n                    <jats:italic>E<\/jats:italic>\n                    )\u20103\u2010alkoxyvinylnitriles were obtained in high yields and with excellent selectivity by simply tuning the steric properties of PNP\u2010pincer ligands: bulkier\n                    <jats:sup>\n                      <jats:italic>t<\/jats:italic>\n                      Bu\n                    <\/jats:sup>\n                    PNP\u2013Mn catalyst favored\n                    <jats:italic>Z<\/jats:italic>\n                    \u2010selectivity, while less hindered\n                    <jats:sup>\n                      <jats:italic>i<\/jats:italic>\n                      Pr\n                    <\/jats:sup>\n                    PNP\u2013Mn catalyst led to\n                    <jats:italic>E<\/jats:italic>\n                    \u2010selectivity. This method features a broad substrate scope, high functional group tolerance and exceptional\n                    <jats:italic>chemo<\/jats:italic>\n                    \u2010,\n                    <jats:italic>regio<\/jats:italic>\n                    \u2010, and\n                    <jats:italic>stereo<\/jats:italic>\n                    \u2010selectivity. Mechanistic studies revealed that\n                    <jats:italic>Z<\/jats:italic>\n                    \u2010products are initially formed in both cases, with the\n                    <jats:sup>\n                      <jats:italic>i<\/jats:italic>\n                      Pr\n                    <\/jats:sup>\n                    PNP\u2013Mn catalyst further promoting isomerization to the thermodynamically favored\n                    <jats:italic>E<\/jats:italic>\n                    \u2010isomers.\n                  <\/jats:p>","DOI":"10.1002\/anie.202511311","type":"journal-article","created":{"date-parts":[[2025,8,1]],"date-time":"2025-08-01T09:32:06Z","timestamp":1754040726000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Ligand\u2010Controlled Stereodivergent Manganese\u2010Catalyzed Hydroalkoxylation of Alkynylnitriles to Access (\n                    <i>E<\/i>\n                    )\u2010 and (\n                    <i>Z<\/i>\n                    )\u20103\u2010Alkoxyvinylnitriles"],"prefix":"10.1002","volume":"64","author":[{"given":"Haobo","family":"Yang","sequence":"first","affiliation":[{"name":"Center of Basic Molecular Science (CBMS) Department of Chemistry Tsinghua University  Beijing 100084 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hui","family":"Huang","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering and Pharmacy Wuhan Institute of Technology  Wuhan Hubei 430205 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4110-5178","authenticated-orcid":false,"given":"Yujie","family":"Wang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Antiviral Drugs Pingyuan Laboratory Henan Normal University  Xinxiang Henan 453007 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4424-6374","authenticated-orcid":false,"given":"Sihui","family":"Long","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering and Pharmacy Wuhan Institute of Technology  Wuhan Hubei 430205 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8402-029X","authenticated-orcid":false,"given":"Qiang","family":"Liu","sequence":"additional","affiliation":[{"name":"Center of Basic Molecular Science (CBMS) Department of Chemistry Tsinghua University  Beijing 100084 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,8]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/asia.202100277"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.0c00851"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5OB00855G"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.202100495"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6RA28598H"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9OB00343F"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.1c01077"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19620951026"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(99)02054-7"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol035918k"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1080\/03086648708080653"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/ajoc.202000336"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1002\/slct.201801522"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200804497"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol500134p"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol300491d"},{"key":"e_1_2_7_17_1","first-page":"973","volume":"41","year":"2005","journal-title":"Chem. 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