{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T02:04:08Z","timestamp":1760234648271,"version":"build-2065373602"},"reference-count":21,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2021,5,28]],"date-time":"2021-05-28T00:00:00Z","timestamp":1622160000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["PTDC\/QUI-QUI\/111288\/2009","UIDB\/04378\/2020"],"award-info":[{"award-number":["PTDC\/QUI-QUI\/111288\/2009","UIDB\/04378\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Applied Sciences"],"abstract":"<jats:p>The reaction mechanism of the Cu+-catalyzed introduction of two all-carbon-substituted stereocenters in an ynamide system using a Grignard reagent, a zinc carbenoid, and an aldehyde, was investigated using density-functional theory. In contrast to the formation of an organocopper(I) compound and subsequent carbocupration reaction, previously postulated as the initial step, the reaction proved to instead proceed through an initial complexation of the substrate alkyne bond by the Cu+-catalyst, which primes this bond for reaction with the Grignard reagent. Subsequent addition of the zinc carbenoid then enables the nucleophilic attack on the incoming aldehyde, which is revealed as the rate-limiting step. Our computations have also identified the factors governing the regio- and setereoselectivity of this interesting reaction, and suggest possible paths for its further development.<\/jats:p>","DOI":"10.3390\/app11115002","type":"journal-article","created":{"date-parts":[[2021,5,28]],"date-time":"2021-05-28T11:33:20Z","timestamp":1622201600000},"page":"5002","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Unveiling the Reaction Mechanism of the Das\/Chechik\/Marek Synthesis of Stereodefined Quaternary Carbon Centers"],"prefix":"10.3390","volume":"11","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9316-9275","authenticated-orcid":false,"given":"Pedro J.","family":"Silva","sequence":"first","affiliation":[{"name":"FP-ENAS\/Faculdade de Ci\u00eancias da Sa\u00fade, Universidade Fernando Pessoa, Rua Carlos da Maia, 296, 4200-150 Porto, Portugal"},{"name":"UCIBIO@REQUIMTE, BioSIM, Departamento de Biomedicina, Faculdade de Medicina, Universidade do Porto, 4200-319 Porto, Portugal"}]},{"given":"Carlos E. P.","family":"Bernardo","sequence":"additional","affiliation":[{"name":"FP-ENAS\/Faculdade de Ci\u00eancias da Sa\u00fade, Universidade Fernando Pessoa, Rua Carlos da Maia, 296, 4200-150 Porto, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2021,5,28]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"128","DOI":"10.1038\/nchem.131","article-title":"A unique approach to aldol products for the creation of all-carbon quaternary stereocentres","volume":"1","author":"Das","year":"2009","journal-title":"Nat. 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