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Yet, accessing\n                    <jats:italic>\u03b1<\/jats:italic>\n                    \u2010tertiary, primary amines (\n                    <jats:italic>\u03b1<\/jats:italic>\n                    \u2010TPAs) remains challenging due to steric congestion and the intrinsic basicity of amine nucleophiles. Although classical nucleophilic\n                    <jats:italic>\u03b1<\/jats:italic>\n                    \u2010amination,\n                    <jats:italic>\u03b1<\/jats:italic>\n                    \u2010C\u2013H functionalization, and photocatalytic\n                    <jats:italic>\u03b1<\/jats:italic>\n                    \u2010NH\n                    <jats:sub>2<\/jats:sub>\n                    radical strategies offer useful platforms, they often suffer from limited functional\u2010group tolerance and poor stereocontrol. Here, we report a streamlined electrochemical difunctionalization strategy that directly transforms 1,1\u2010disubstituted alkenes into C(\n                    <jats:italic>sp<\/jats:italic>\n                    <jats:sup>3<\/jats:sup>\n                    )\u2010rich\n                    <jats:italic>\u03b1<\/jats:italic>\n                    \u2010TPAs using inexpensive and bench\u2010stable ammonium surrogates. This metal\u2010 and oxidant\u2010free aminochalcogenation employs thiophenols as the most user\u2010friendly thiolating agents, avoiding pre\u2010activated sulphur reagents and enabling efficient aminosulfenylation and aminoselenylation in a single operation. The strategy accommodates diverse\n                    <jats:italic>N<\/jats:italic>\n                    \u2010sources, including ammonia surrogate, amino acids, dipeptides, aliphatic amines, and\n                    <jats:italic>N<\/jats:italic>\n                    \u2010heterocycles, enabling the synthesis of\n                    <jats:italic>\u03b1<\/jats:italic>\n                    \u2010tertiary, primary as well as secondary amines and facilitating late\u2010stage functionalization of pharmaceutically relevant scaffolds (&gt; 71 examples and up to 82% yield). The robustness of the strategy was further demonstrated by an efficient gram\u2010scale electrolysis. This work provides a modular, sustainable route to free alkyl amines that remain difficult to access by conventional methods.\n                  <\/jats:p>","DOI":"10.1002\/anie.9487272","type":"journal-article","created":{"date-parts":[[2026,8,13]],"date-time":"2026-08-13T16:01:26Z","timestamp":1786636886000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Modular Access to\n                    <i>\u03b1<\/i>\n                    \u2010Tertiary Amines: Electrochemical Tandem Di\u2010Functionalization of Olefins With Ammonia Surrogates and Amino Acids"],"prefix":"10.1002","volume":"65","author":[{"given":"Adrija","family":"Ghosh","sequence":"first","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Roorkee  Roorkee Uttarakhand India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"family":"Tarun","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Roorkee  Roorkee Uttarakhand India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0006-8239-6839","authenticated-orcid":false,"given":"Sven Erik","family":"Peters","sequence":"additional","affiliation":[{"name":"Institute of Organic and Biomolecular Chemistry Georg\u2010August\u2010Universit\u00e4t G\u00f6ttingen  G\u00f6ttingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7034-8772","authenticated-orcid":false,"given":"Lutz","family":"Ackermann","sequence":"additional","affiliation":[{"name":"Institute of Organic and Biomolecular Chemistry Georg\u2010August\u2010Universit\u00e4t G\u00f6ttingen  G\u00f6ttingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8626-8742","authenticated-orcid":false,"given":"Debasis","family":"Banerjee","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Roorkee  Roorkee Uttarakhand India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,8,13]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/jm901241e"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.1015024108"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2md20347b"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41586\u2010019\u20101179\u20102"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jmedchem.0c00829"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja410424g"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature14007"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jmedchem.0c00754"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ed1003806"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/c1cc00049g"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5NP00096C"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.3c02507"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.31635\/ccschem.023.202302999"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr940474e"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1039\/b617746h"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201609963"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201710084"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8SC05164J"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010022\u201030281\u2010z"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo001179z"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr900382t"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-0030-1258893"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1038\/nprot.2013.134"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.202400350"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.9b05011"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.3c01474"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202005294"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b10871"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c07402"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.3762\/bjoc.17.112"},{"key":"e_1_2_8_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja1036226"},{"key":"e_1_2_8_33_1","first-page":"3795","article-title":"Hydroamination: Direct Addition of Amines to Alkenes and Alkynes","volume":"108","author":"M\u00fcller T. 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