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Here, we disclosed an efficient and straightforward cascade reaction between ethynyl ketones and phosphine oxides, resulting in a broad array of trisubstituted allenes incorporating a phosphorus moiety in high yields with excellent stereoselectivities facilitated by peptide\u2010mimic phosphonium salt (PPS) catalysis, Additionally, comprehensive series of mechanistic experiments have been conducted to elucidate that this cascade reaction proceeds via an asymmetric Pudovik addition reaction followed by a subsequent\n                    <jats:italic>phospha<\/jats:italic>\n                    \u2010Brook rearrangement that occurs concomitantly with kinetic resolution, representing a stereospecific rearrangement and protonation process facilitating central\u2010to\u2010axial chirality transfer in a cascade manner. We anticipate that our research will pave the way for a promising exploration of novel stereo\u2010induction pattern in the Pudovik addition\/\n                    <jats:italic>phospha<\/jats:italic>\n                    \u2010Brook rearrangement cascade reaction.\n                  <\/jats:p>","DOI":"10.1002\/anie.202403707","type":"journal-article","created":{"date-parts":[[2024,3,23]],"date-time":"2024-03-23T06:38:38Z","timestamp":1711175918000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":35,"title":["Novel Stereo\u2010Induction Pattern in Pudovik Addition\/\n                    <i>Phospha<\/i>\n                    \u2010Brook Rearrangement Towards Chiral Trisubstituted Allenes"],"prefix":"10.1002","volume":"63","author":[{"given":"Jia\u2010Yan","family":"Zheng","sequence":"first","affiliation":[{"name":"Key Laboratory of Green Chemistry &amp; Technology of Ministry of Education College of Chemistry Sichuan University  29 Wangjiang Road Chengdu 610064 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fan","family":"Wang","sequence":"additional","affiliation":[{"name":"Key Laboratory of Green Chemistry &amp; Technology of Ministry of Education College of Chemistry Sichuan University  29 Wangjiang Road Chengdu 610064 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yan","family":"Zhang","sequence":"additional","affiliation":[{"name":"Key Laboratory of Green Chemistry &amp; Technology of Ministry of Education College of Chemistry Sichuan University  29 Wangjiang Road Chengdu 610064 P. R. 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