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This enantioconvergent reaction utilizes racemic allenylic alcohol as the electrophile and shows compatibility with a variety of electron\u2010rich arenes and heteroarenes. The resulting highly enantioenriched (up to &gt;99.5\u2009:\u20090.5 e.r.) 1,1\u2010disubstituted allenylic methanes, bearing a benzylic carbon stereocenter, are obtained with complete regiocontrol \u2013 both on (hetero)arenes as well as on the allenylic fragment. This protocol allows for the enantioselective formal introduction of a 4\u2010carbon alkyl chain into (hetero)arenes, along with the creation of a benzylic stereocenter. Judicious synthetic elaborations not only lead to formal enantioselective FC alkylation products of less electron\u2010rich arenes but also of substituted arenes in <jats:italic>ortho<\/jats:italic>\u2010 and even <jats:italic>meta<\/jats:italic>\u2010selective fashion. An intramolecular version of this FC allenylation is shown to proceed with promising enantioselectivity under the same catalytic conditions. Mechanistic studies revealed the involvement of dynamic kinetic asymmetric transformation (DyKAT) of racemic allenylic alcohols in this reaction.<\/jats:p>","DOI":"10.1002\/anie.202413609","type":"journal-article","created":{"date-parts":[[2024,8,7]],"date-time":"2024-08-07T05:57:17Z","timestamp":1723010237000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Catalytic Enantioselective Friedel\u2013Crafts Allenylation"],"prefix":"10.1002","volume":"63","author":[{"ORCID":"https:\/\/orcid.org\/0009-0009-7215-8222","authenticated-orcid":false,"given":"Priyotosh","family":"Das","sequence":"first","affiliation":[{"name":"Department of Organic Chemistry Indian Institute of Science  Bangalore 560 012 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0005-4681-6579","authenticated-orcid":false,"given":"Debangshu","family":"Ghosh","sequence":"additional","affiliation":[{"name":"Department of Organic Chemistry Indian Institute of Science  Bangalore 560 012 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9651-6228","authenticated-orcid":false,"given":"Santanu","family":"Mukherjee","sequence":"additional","affiliation":[{"name":"Department of Organic Chemistry Indian Institute of Science  Bangalore 560 012 India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,10,14]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ed1003806"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja025981p"},{"key":"e_1_2_7_4_1","unstructured":"\u00a0"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.1c00220"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202011901"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.abd5992"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscentsci.0c01413"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1038\/s43586-021-00041-2"},{"key":"e_1_2_7_10_1","first-page":"1392","volume":"84","author":"Friedel C.","year":"1877","journal-title":"Compt. 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