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Deuteration experiments and kinetic isotope effect measurements revealed major mechanistic differences to related Rh<jats:sup>I<\/jats:sup>\u2010catalyzed transformations. Supported by DFT calculations we propose the initial formation of an Ir<jats:sup>III<\/jats:sup> hydride intermediate, which then undergoes a \u03b2\u2010C elimination (C\u2212C bond activation) prior to reductive C\u2212H elimination. The computational model also allows the prediction of the stereochemical outcome. The Ir\u2010catalyzed cyclobutanol cleavage is broadly applicable but fails for substrates bearing strongly coordinating groups. The method is of particular value for the stereo\u2010controlled synthesis of substituted chromanes related to the tocopherols and other natural products.<\/jats:p>","DOI":"10.1002\/chem.202004843","type":"journal-article","created":{"date-parts":[[2020,12,13]],"date-time":"2020-12-13T22:08:48Z","timestamp":1607897328000},"page":"4640-4652","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Enantioselective Cleavage of Cyclobutanols Through Ir\u2010Catalyzed C\u2212C Bond Activation: Mechanistic and Synthetic Aspects"],"prefix":"10.1002","volume":"27","author":[{"given":"Friederike","family":"Ratsch","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Cologne  Greinstra\u00dfe 4 50939 K\u00f6ln Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Joss Pepe","family":"Strache","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Cologne  Greinstra\u00dfe 4 50939 K\u00f6ln Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Waldemar","family":"Schlundt","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Cologne  Greinstra\u00dfe 4 50939 K\u00f6ln Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"J\u00f6rg\u2010Martin","family":"Neud\u00f6rfl","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Cologne  Greinstra\u00dfe 4 50939 K\u00f6ln Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Andreas","family":"Adler","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Cologne  Greinstra\u00dfe 4 50939 K\u00f6ln Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sarwar","family":"Aziz","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Cologne  Greinstra\u00dfe 4 50939 K\u00f6ln Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1814-8818","authenticated-orcid":false,"given":"Bernd","family":"Goldfuss","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Cologne  Greinstra\u00dfe 4 50939 K\u00f6ln Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0489-1827","authenticated-orcid":false,"given":"Hans\u2010G\u00fcnther","family":"Schmalz","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Cologne  Greinstra\u00dfe 4 50939 K\u00f6ln Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2021,2,3]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00138"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature19849"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201101616"},{"key":"e_1_2_7_5_2","first-page":"163","volume-title":"Asymmetric Transformations via C\u2212C Bond Cleavage, published in: C\u2212C Bond Activation, Vol.\u2005346","author":"Souillart L.","year":"2014"},{"volume-title":"Cleavage of Carbon-Carbon Single Bonds by Transition Metals","year":"2016","author":"Murakami M.","key":"e_1_2_7_6_2"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1039\/b904405a"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2004.06.100"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1038\/370540a0"},{"key":"e_1_2_7_10_1","unstructured":"\u00a0"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol301280u"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja502601g"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja971949x"},{"key":"e_1_2_7_14_1","first-page":"1","volume-title":"Mechanistic Studies of Transition Metal-Mediated C\u2212C Bond Activation, published in: C\u2212C Bond Activation, Vol.\u2005346","author":"Jones W. 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