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A fundamental challenge lies in balancing the high ambiphilic reactivity required for transfer with the requisite molecular stability. Herein, we report the synthesis of a series of bisphosphane\u2010stabilized borylenes and disclose their exceptional borylene\u2010transfer capabilities. The target borylenes (\n                    <jats:bold>3<\/jats:bold>\n                    ) were prepared via facile deprotonation of the corresponding bisphosphane\u2010coordinated hydroboronium precursors using KHMDS (potassium bis(trimethylsilyl)amide). Notably, borylene\n                    <jats:bold>3a<\/jats:bold>\n                    undergoes formal B\u2500H bond insertion with hydroboranes to yield diborane (6) derivatives. Furthermore,\n                    <jats:bold>3a<\/jats:bold>\n                    facilitates unprecedented borylene transfer to polar \u03c0 systems, including benzaldehyde and chalcone, providing efficient access to three\u2010membered oxaboriranes and boriranes. Experimental and computational studies reveal that the labile phosphorus\u2013boron (P\u2013B) coordination is pivotal in maintaining the high borylene\u2010transfer capability of\n                    <jats:bold>3a<\/jats:bold>\n                    . These preliminary results set the stage for the use of stable hydroboronium compounds as practical borylene\u2010transfer reagent precursors in synthetic chemistry.\n                  <\/jats:p>","DOI":"10.1002\/anie.2903979","type":"journal-article","created":{"date-parts":[[2026,6,18]],"date-time":"2026-06-18T17:48:02Z","timestamp":1781804882000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Bisphosphane\u2010Stabilized Borylenes: Unlocking Borylene Transfer Reactivities"],"prefix":"10.1002","volume":"65","author":[{"given":"Zimeng","family":"Zhang","sequence":"first","affiliation":[{"name":"Key Laboratory of Organic Synthesis of Jiangsu Province College of Chemistry Chemical Engineering and Materials Science Soochow University Renai Road 199 Suzhou Jiangsu Province P. R. 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