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In contrast, main group\u2010mediated strategies remain underdeveloped, with those reported generally limited to activated substrates and harsh reaction conditions. Here, a new sodium\u2010mediated protocol for deprotonative C(\n                    <jats:italic>sp<\/jats:italic>\n                    <jats:sup>3<\/jats:sup>\n                    )\/C(\n                    <jats:italic>sp<\/jats:italic>\n                    <jats:sup>2<\/jats:sup>\n                    )\u2013H silylation of (hetero)arenes is presented, which relies on the power of the strongly basic sodium amide NaTMP (TMP = 2,2,6,6\u2010tetramethylpiperidide) in combination with bulky chlorosilanes. This approach provides direct access to a myriad of silylated aromatic products, including toluene derivatives, non\u2010activated arenes such as benzene and naphthalene, pyridines and electron\u2010rich heterocycles. Mechanistic investigations, combining the isolation of key organometallic intermediates with theoretical calculations, underline the complementarity of NaTMP and the electrophilic chlorosilane, and reveal the steric and coordination effects that govern sodiation and silylation steps. Most notably, this protocol extends beyond conventional monosilylation, including orthogonal multisilylation of distinct C(\n                    <jats:italic>sp<\/jats:italic>\n                    <jats:sup>3<\/jats:sup>\n                    ) and C(\n                    <jats:italic>sp<\/jats:italic>\n                    <jats:sup>2<\/jats:sup>\n                    )\u2013H bonds, thereby broadening the scope of main group\u2010mediated arene functionalization.\n                  <\/jats:p>","DOI":"10.1002\/anie.1774364","type":"journal-article","created":{"date-parts":[[2026,4,10]],"date-time":"2026-04-10T03:43:34Z","timestamp":1775792614000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Deprotonative C(\n                    <i>sp<\/i>\n                    <sup>3<\/sup>\n                    )\/C(\n                    <i>sp<\/i>\n                    <sup>2<\/sup>\n                    )\u2013H (Multi)Silylation of (Hetero)Arenes Mediated by NaTMP"],"prefix":"10.1002","volume":"65","author":[{"given":"David","family":"S\u00e1nchez\u2010Roa","sequence":"first","affiliation":[{"name":"Department F\u00fcr Chemie, Biochemie und Pharmacie Universit\u00e4t Bern  Bern Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sophia","family":"Belrhomari","sequence":"additional","affiliation":[{"name":"Department F\u00fcr Chemie, Biochemie und Pharmacie Universit\u00e4t Bern  Bern Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ana","family":"McGinley","sequence":"additional","affiliation":[{"name":"School of Chemistry Trinity College Dublin College Green  Dublin 2 Ireland"},{"name":"Parque Tecnol\u00f3gico de \u00c1lava  Vitoria\u2010Gasteiz Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Clevin Anto","family":"Liju","sequence":"additional","affiliation":[{"name":"School of Chemistry Trinity College Dublin College Green  Dublin 2 Ireland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Manting","family":"Mu","sequence":"additional","affiliation":[{"name":"School of Chemistry Trinity College Dublin College Green  Dublin 2 Ireland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1348-4692","authenticated-orcid":false,"given":"Max","family":"Garc\u00eda\u2010Melchor","sequence":"additional","affiliation":[{"name":"School of Chemistry Trinity College Dublin College Green  Dublin 2 Ireland"},{"name":"Parque Tecnol\u00f3gico de \u00c1lava  Vitoria\u2010Gasteiz Spain"},{"name":"Basque Foundation for Science  Bilbao Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3998-7506","authenticated-orcid":false,"given":"Eva","family":"Hevia","sequence":"additional","affiliation":[{"name":"Department F\u00fcr Chemie, Biochemie und Pharmacie Universit\u00e4t Bern  Bern 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