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A copper\u2010mediated 1,4\u2010Brook rearrangement converts the resulting alkenylsilanes into alkenylcopper species, which can be intercepted with a multitude of carbon\u2010 or heteroatom\u2010based electrophiles; this formal\n                    <jats:italic>ipso<\/jats:italic>\n                    \u2010substitution of the R\n                    <jats:sub>3<\/jats:sub>\n                    Si\u2010group allows a variety of trisubstituted olefins to be formed in stereodefined format, including fluoroalkenes and olefins bearing trifluoromethyl substituents. Best results are obtained with copper amides such as [Cu(NEt\n                    <jats:sub>2<\/jats:sub>\n                    )]\n                    <jats:sub>4<\/jats:sub>\n                    as the promoter in THF\/DMPU; they are sufficiently basic to deprotonate the \u2500OH group in the first place, thereby triggering the critically important C\u2010to\u2010O silyl migration, yet mild enough to ensure compatibility with a variety of functional groups, including even C\u2500H acidic sites adjacent to an ester or ketone. In cases where the trapping of the organocopper intermediates primarily formed is unduly slow or inefficient, the addition of either 2\u2010thienyllithium or tetra\u2010\n                    <jats:italic>n<\/jats:italic>\n                    \u2010butylammonium cyanide is recommended; these additives lead to more highly nucleophilic cuprate species that show the right reactivity profile for efficient coupling of otherwise noncompliant electrophilic partners.\n                  <\/jats:p>","DOI":"10.1002\/anie.8014602","type":"journal-article","created":{"date-parts":[[2026,9,11]],"date-time":"2026-09-11T05:38:07Z","timestamp":1789105087000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["1,4\u2010Brook Rearrangement of \u03b2\u2010Silyl Allylic Alcohols: Trisubstituted Alkenes by Copper\u2010Mediated Stereoretentive\n                    <i>ipso<\/i>\n                    \u2010Substitution Reactions"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0009-0004-3510-2346","authenticated-orcid":false,"given":"Paul","family":"Haf\u2010Moths","sequence":"first","affiliation":[{"name":"Max\u2010Planck\u2010Institut f\u00fcr Kohlenforschung  M\u00fclheim Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9386-6476","authenticated-orcid":false,"given":"Jack L.","family":"Sutro","sequence":"additional","affiliation":[{"name":"Max\u2010Planck\u2010Institut f\u00fcr Kohlenforschung  M\u00fclheim Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0098-3417","authenticated-orcid":false,"given":"Alois","family":"F\u00fcrstner","sequence":"additional","affiliation":[{"name":"Max\u2010Planck\u2010Institut f\u00fcr Kohlenforschung  M\u00fclheim 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