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Despite widespread interest in this process, asymmetric variants have previously relied upon stoichiometric chiral auxiliary or chirality transfer strategies to induce stereocontrol. In this manuscript, the organocatalytic enantioselective Sommelet\u2013Hauser rearrangement of ammonium ylides bearing heteroaromatic substituents is demonstrated using a Lewis basic isothiourea catalyst, providing a series of unnatural \u03b1-heteroaryl \u03b1-amino acid derivatives with high to excellent enantioselectivity (up to 98:2 er). The developed process tolerates cyclic and acyclic ammonium salt precursors with indolyl and benzofuranyl substituents. A range of pronucleophiles was employed that lead to amide, ester, and alcohol products. Computational analysis revealed that a stepwise process (involving initial C\u2013N bond cleavage to generate an ion pair, followed by a barrierless C\u2013C bond formation) is favored over a concerted [2,3]-rearrangement, with distortion-interaction analysis providing insight into the factors that govern the mechanism. Crossover experiments, including the use of isotopologue salt derivatives to minimize chemical differentiation of substrates, showed no scrambling. The totality of accumulated computational and experimental evidence suggests a stepwise rearrangement involving a near-instantaneous second recombination step such that the overall process is indistinguishable from, and effectively, a concerted asynchronous rearrangement.<\/jats:p>","DOI":"10.1021\/jacs.6c04476","type":"journal-article","created":{"date-parts":[[2026,8,6]],"date-time":"2026-08-06T16:01:24Z","timestamp":1786032084000},"page":"34161-34172","source":"Crossref","is-referenced-by-count":0,"title":["The Catalytic Enantioselective\nSommelet\u2013Hauser\nRearrangement"],"prefix":"10.1021","volume":"148","author":[{"given":"Ihssane","family":"El Fdali","sequence":"first","affiliation":[{"name":"University of St Andrews , , North Haugh , ,","place":["St Andrews, United Kingdom, KY16 9ST"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jacqueline M.","family":"Laddusaw","sequence":"additional","affiliation":[{"name":"Oregon State University , , 153 Gilbert Hall , , ,","place":["Corvallis, Oregon, United States, 97331"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1298-8784","authenticated-orcid":true,"given":"Kevin","family":"Kasten","sequence":"additional","affiliation":[{"name":"University of St Andrews , , North Haugh , ,","place":["St Andrews, United Kingdom, KY16 9ST"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8578-7054","authenticated-orcid":true,"given":"Aidan P.","family":"McKay","sequence":"additional","affiliation":[{"name":"University of St Andrews , , North Haugh , ,","place":["St Andrews, United Kingdom, KY16 9ST"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5366-9168","authenticated-orcid":true,"given":"David B.","family":"Cordes","sequence":"additional","affiliation":[{"name":"University of St Andrews , , North Haugh , ,","place":["St Andrews, United Kingdom, KY16 9ST"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Paul Ha-Yeon","family":"Cheong","sequence":"additional","affiliation":[{"name":"Oregon State University , , 153 Gilbert Hall , , ,","place":["Corvallis, Oregon, United States, 97331"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2104-7313","authenticated-orcid":true,"given":"Andrew D.","family":"Smith","sequence":"additional","affiliation":[{"name":"University of St Andrews , , North Haugh , ,","place":["St Andrews, United Kingdom, KY16 9ST"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,6]]},"reference":[{"key":"2026081910210258700_cit1","volume-title":"Comprehensive\nOrganic Synthesis. 1: Additions to C-X pi-Bonds, Part 1\/Vol. ed.:\nStuart L. 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Soc."},{"key":"2026081910210258700_cit35","article-title":"On a particular\nmode of intramolecular rearrangement","volume":"205","author":"Sommelet","year":"1937","journal-title":"Compt.\nRend."},{"key":"2026081910210258700_cit36","doi-asserted-by":"publisher","first-page":"4122","DOI":"10.1021\/ja01153a022","article-title":"Rearrangements of\nBenzyltrimethylammonium Ion and Related\nQuaternary Ammonium Ions by Sodium Amide Involving Migration into\nthe Ring","volume":"73","author":"Kantor","year":"1951","journal-title":"J. Am. Chem. 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