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A racemic variant of the reaction is synergistically promoted by catalytic N\u2010heterocyclic carbene (NHC) and organic base, whereas chiral amino alcohol\u2010derived bifunctional NHC enables a catalytic enantioselective variant. The reaction likely involves the generation of enolized zinc homoenolate via ring\u2010opening of zinc cyclopropoxide and enolization of the resulting homoenolate, followed by its addition to the cyclopropene as a prochiral allylzinc nucleophile. Our mechanistic investigations highlighted the transient nature of enolized homoenolate, which, once generated from thermodynamically predominant cyclopropoxide, immediately proceeds to allylzincation with cyclopropene. The NHC not only promotes the rate\u2010determining generation of enolized homoenolate but also engages in the allylzincation process. The resulting cyclopropylzinc species undergoes partial in situ protonation while partially remaining intact, thereby leaving an opportunity for trapping with an external electrophile.<\/jats:p>","DOI":"10.1002\/anie.202412456","type":"journal-article","created":{"date-parts":[[2024,8,6]],"date-time":"2024-08-06T22:24:26Z","timestamp":1722983066000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["Stereoselective Hydroxyallylation of Cyclopropenes with Cyclopropanols via NHC Catalysis of Transient Organozinc Species"],"prefix":"10.1002","volume":"63","author":[{"given":"Kento","family":"Tsukiji","sequence":"first","affiliation":[{"name":"Graduate School of Pharmaceutical Sciences Tohoku University  6-3 Aoba, Aramaki 980-8578 Sendai 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These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."},{"key":"e_1_2_7_86_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.2c04010"},{"key":"e_1_2_7_87_1","unstructured":"\u00a0"},{"key":"e_1_2_7_88_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c01133"},{"key":"e_1_2_7_89_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c01695"},{"key":"e_1_2_7_90_1","unstructured":"\u00a0"},{"key":"e_1_2_7_91_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202004222"},{"key":"e_1_2_7_92_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-020-0421-8"},{"key":"e_1_2_7_93_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201609757"},{"key":"e_1_2_7_94_1","unstructured":"A second hypothesis that is accelerated enolization of NHC-boundB2nwithA2nmay not be excluded. However we prefer the first hypothesis as we suspect that the coordination of NHC toB2nmay not necessarily increase the acidity of the \u03b1-proton. Note also that from the DFT calculations (Scheme\u2005S4) the combination of NHC-bound cyclopropoxide and NHC-unbound homoenolate is suggested to be thermodynamically more favored than the opposite combination."},{"key":"e_1_2_7_95_1","unstructured":"Interestingly deuterium incorporation was also observed at theorthopositions of the phenyl group of the hydroxyallyl moiety (see the Supporting Information)."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202412456","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,4,4]],"date-time":"2025-04-04T20:00:10Z","timestamp":1743796810000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202412456"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,10,8]]},"references-count":95,"journal-issue":{"issue":"46","published-print":{"date-parts":[[2024,11,11]]}},"alternative-id":["10.1002\/anie.202412456"],"URL":"https:\/\/doi.org\/10.1002\/anie.202412456","archive":["Portico"],"relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv-2023-hch07-v2","asserted-by":"object"}]},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,10,8]]},"assertion":[{"value":"2024-07-02","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2024-10-08","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202412456"}}