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Here, we present a mild and scalable Sc(OTf)\n                    <jats:sub>3<\/jats:sub>\n                    \u2010catalyzed [3+2] cycloaddition of bicyclo[1.1.0]butanes (BCBs) with ynamides, yielding a diverse array of polysubstituted 2\u2010amino\u2010bicyclo[2.1.1]hexenes in good to excellent yields. These products offer valuable starting materials for the construction of novel functionalized bicyclo[1.1.0]butanes. Preliminary mechanistic studies indicate that the reaction involves a nucleophilic addition of ynamides to bicyclo[1.1.0]butanes, followed by an intramolecular cyclization of in situ generated enolate and keteniminium ion. We expect that these findings will encourage utilization of complex bioisosteres and foster further investigation into BCB\u2010based cycloaddition chemistry.\n                  <\/jats:p>","DOI":"10.1002\/anie.202405781","type":"journal-article","created":{"date-parts":[[2024,5,23]],"date-time":"2024-05-23T22:24:52Z","timestamp":1716503092000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":82,"title":["Lewis Acid Catalyzed Cycloaddition of Bicyclobutanes with Ynamides for the Synthesis of Polysubstituted 2\u2010Amino\u2010bicyclo[2.1.1]hexenes"],"prefix":"10.1002","volume":"63","author":[{"given":"Qian\u2010Qian","family":"Hu","sequence":"first","affiliation":[{"name":"Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry &amp; Materials Science Northwest University  Xi'an 710127 P. R. 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