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We also extend this reactivity to the dual use of hexamethyldisilazide (HMDS) reagents as bases and nucleophilic ammonia surrogates to access primary benzyl amines via a simple deprotection and isolation protocol. This methodology leverages halogen transfer (X-transfer) reactivity to merge deprotonation, halogenation, and nucleophilic substitution into one synergistic process that is critical for reaction success. Here, a thermodynamically uphill deprotonation event generates transient benzyl carbanionic and halide intermediates which circumvent well-known complications of dimerization in metalation-halogenation sequences and amine overalkylation from benzyl halide substitution. These features enable novel scope and selectivity opportunities over traditional C\u2013H metalation chemistry and established radical- or nitrene-based C\u2013H amination strategies. With reactivity guided by C\u2013H acidity trends, this protocol is effective for polyalkylarenes, hard-to-oxidize alkyl(hetero)arenes, and substrates with oxidation-prone functional groups that are unsuitable or unselective in alternative mechanistic approaches. New benzofuran and indole X-transfer reagents (XTRs), which are compatible with amine nucleophiles and bases, allow the expansion of X-transfer oxidative coupling to a substantially wider pKa range than previously accessible. Structural studies of these easily-prepared reagents explain their enhanced productivity for C\u2013H amination and provide guidelines for their continued application to other oxidative C\u2013H coupling reactions.<\/jats:p>","DOI":"10.1021\/jacs.6c09674","type":"journal-article","created":{"date-parts":[[2026,7,21]],"date-time":"2026-07-21T17:11:31Z","timestamp":1784653891000},"page":"32542-32555","source":"Crossref","is-referenced-by-count":0,"title":["Base-Promoted Benzylic C\u2013H Amination Reactions Across a Wide p\n                    <i>K<\/i>\n                    a Spectrum Enabled by 2-Halobenzofuran and -Indole Oxidants"],"prefix":"10.1021","volume":"148","author":[{"ORCID":"https:\/\/orcid.org\/0009-0005-4113-582X","authenticated-orcid":true,"given":"Vivian N.","family":"Nguyen","sequence":"first","affiliation":[{"name":"Colorado State University , , , ,","place":["Fort Collins, Colorado, United States, 80523"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Garrett A.","family":"Hoteling","sequence":"additional","affiliation":[{"name":"Colorado State University , , , ,","place":["Fort Collins, Colorado, United States, 80523"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Michael D.","family":"Delost","sequence":"additional","affiliation":[{"name":"Colorado State University , , , ,","place":["Fort Collins, Colorado, United States, 80523"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kayla L.","family":"Constantini","sequence":"additional","affiliation":[{"name":"Colorado State University , , , ,","place":["Fort Collins, Colorado, United States, 80523"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"William B.","family":"Hughes","sequence":"additional","affiliation":[{"name":"Colorado State University , , , ,","place":["Fort Collins, Colorado, United States, 80523"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0104-4166","authenticated-orcid":true,"given":"Robert S.","family":"Paton","sequence":"additional","affiliation":[{"name":"Colorado State University , , , ,","place":["Fort Collins, Colorado, United States, 80523"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5418-3082","authenticated-orcid":true,"given":"Jeffrey S.","family":"Bandar","sequence":"additional","affiliation":[{"name":"Colorado State University , , , ,","place":["Fort Collins, Colorado, United States, 80523"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,21]]},"reference":[{"key":"2026081012064926800_cit1a","doi-asserted-by":"publisher","first-page":"9247","DOI":"10.1021\/acs.chemrev.6b00644","article-title":"Transition Metal-Catalyzed C\u2013H Amination: Scope, Mechanism, and Applications","volume":"117","author":"Park","year":"2017","journal-title":"Chem. 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