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The method employs a chiral NHC\u2212Cu catalyst capable of generating in a single step chiral skipped dienes bearing a <jats:italic>Z<\/jats:italic>\u2010alkenyl chloride, a trisubstituted <jats:italic>E<\/jats:italic>\u2010alkenyl boronate and a bis\u2010allylic stereocenter with excellent levels of chemo\u2010, regio\u2010 enantio\u2010 and diastereoselectivity. This high degree of functionalization makes these products versatile building blocks as illustrated with the synthesis of several optically active compounds. DFT calculations support the key presence of a metal cation bridge ligand\u2013substrate interaction and account for the stereoselectivity outcome.<\/jats:p>","DOI":"10.1002\/anie.202117696","type":"journal-article","created":{"date-parts":[[2022,3,9]],"date-time":"2022-03-09T19:00:19Z","timestamp":1646852419000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":30,"title":["Enantio\u2010 and Diastereoselective Copper\u2010Catalyzed Allylboration of Alkynes with Allylic <i>gem<\/i>\u2010Dichlorides"],"prefix":"10.1002","volume":"61","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-7216-2023","authenticated-orcid":false,"given":"Andrea","family":"Chaves\u2010Pouso","sequence":"first","affiliation":[{"name":"Centro Singular de Investigaci\u00f3n en Qu\u00edmica Biol\u00f3xica e Materiais Moleculares (CiQUS) Departamento de Qu\u00edmica Org\u00e1nica Universidade de Santiago de Compostela  15782 Santiago de Compostela Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8948-1258","authenticated-orcid":false,"given":"Andr\u00e9s M.","family":"\u00c1lvarez\u2010Constantino","sequence":"additional","affiliation":[{"name":"Centro Singular de Investigaci\u00f3n en Qu\u00edmica Biol\u00f3xica e Materiais Moleculares (CiQUS) Departamento de Qu\u00edmica Org\u00e1nica Universidade de Santiago de Compostela  15782 Santiago de Compostela Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4903-0502","authenticated-orcid":false,"given":"Mart\u00edn","family":"Fa\u00f1an\u00e1s\u2010Mastral","sequence":"additional","affiliation":[{"name":"Centro Singular de Investigaci\u00f3n en Qu\u00edmica Biol\u00f3xica e Materiais Moleculares (CiQUS) Departamento de Qu\u00edmica Org\u00e1nica Universidade de Santiago de Compostela  15782 Santiago de Compostela 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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_3_50_1","unstructured":"Allylicgem-dichlorides are readily obtained from the corresponding \u03b1 \u03b2-unsaturated aldehyde by reaction with SOCl2or oxalyl chloride (see the Supporting Information for details)."},{"key":"e_1_2_3_51_1","unstructured":"Allylic 1 3-dichlorides seemed not to participate in the reaction and were recovered with partial decomposition. For the synthesis of products22and24 the corresponding allylic 1 3-dichloride were recovered in 37\u2009% and 99\u2009% respectively. 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For further details see the Supporting Information."},{"key":"e_1_2_3_59_1","unstructured":"\u00a0"},{"key":"e_1_2_3_60_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1676210"},{"key":"e_1_2_3_61_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1096-987X(19990115)20:1<114::AID-JCC12>3.0.CO;2-L"},{"key":"e_1_2_3_62_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0734086"},{"key":"e_1_2_3_63_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202107004"},{"key":"e_1_2_3_63_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202107004"},{"key":"e_1_2_3_64_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201701486"},{"key":"e_1_2_3_64_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201701486"},{"key":"e_1_2_3_65_1","unstructured":"Energy differences (\u0394\u0394E\u2260) between each pair of transition states were divided into contributions from the distortions of both the NHC\u2212Cu-alkenylboronate and the allylicgem-dichloride into the transition state structures (\u0394\u0394E\u2260dist) and the contributions in noncovalent interactions between the NHC\u2212Cu-alkenylboronate and the allylicgem-dichloride (\u0394\u0394E\u2260int). 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