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In this paper, the copper\u2010catalyzed enantioselective hydrosilylation of <jats:italic>gem<\/jats:italic>\u2010difluorocyclopropenes to provide the corresponding chiral <jats:italic>gem<\/jats:italic>\u2010difluorocyclopropanes is presented. The use of copper(I) chloride, chiral ligands including bidentate BINAPs and monodentate phosphoramidites, and silylborane Me<jats:sub>2<\/jats:sub>PhSi\u2010Bpin accompanying sodium <jats:italic>tert<\/jats:italic>\u2010butoxide in methanol was appropriate for the enantioselective hydrosilylation of the strained C=C double bond, and the resultant chiral difluorinated three\u2010membered ring was unambiguously characterized. Subsequent activation of the silyl groups in enantio\u2010enriched <jats:italic>gem<\/jats:italic>\u2010difluorocyclopropanes showed substantial reduction of the enantiopurity, indicating cleavage of the distal C\u2212C bond leading to the transient acyclic intermediates.<\/jats:p>","DOI":"10.1002\/chem.202200657","type":"journal-article","created":{"date-parts":[[2022,4,8]],"date-time":"2022-04-08T02:02:51Z","timestamp":1649383371000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":22,"title":["Copper\u2010Catalyzed Enantioselective Hydrosilylation of <i>gem<\/i>\u2010Difluorocyclopropenes Leading to a Stereochemical Study of the Silylated <i>gem<\/i>\u2010Difluorocyclopropanes"],"prefix":"10.1002","volume":"28","author":[{"given":"Keisuke","family":"Sekine","sequence":"first","affiliation":[{"name":"Department of Applied Chemistry School of Materials and Chemical Technology Tokyo Institute of Technology  2-12-1-H113 Ookayama Meguro-ku Tokyo 152-8552 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dai","family":"Akaishi","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry School of Materials and Chemical Technology Tokyo Institute of Technology  2-12-1-H113 Ookayama Meguro-ku Tokyo 152-8552 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kakeru","family":"Konagaya","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry School of Materials and Chemical Technology Tokyo Institute of Technology  2-12-1-H113 Ookayama Meguro-ku Tokyo 152-8552 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5737-8499","authenticated-orcid":false,"given":"Shigekazu","family":"Ito","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry School of Materials and Chemical Technology Tokyo Institute of Technology  2-12-1-H113 Ookayama Meguro-ku Tokyo 152-8552 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,5,2]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198603121"},{"key":"e_1_2_7_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19860980405"},{"key":"e_1_2_7_2_1","doi-asserted-by":"crossref","unstructured":"O.\u2005G. 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