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In contrast, the chemical behavior of alkynyl triazenes upon irradiation with light is still unknown. Herein we present the first photoactivation of alkynyl triazenes that triggers an uncommon reactivity pattern involving the cleavage of the N1\u2212N2 bond of the triazene moiety resulting in a unique approach to cyanocarbenes from a readily available, stable, and insensitive precursor. This allows to access various nitrile compounds without the use of a toxic cyanating agent by exploiting the reactivity pattern of carbenes. By variation of the reaction conditions and light sources, different substitution patterns can be obtained selectively in good yields under mild and metal\u2010free conditions, thus introducing the alkynyl triazene unit as a photo accessible methylene nitrile synthon. Using this synthon, subclasses like \u03b1\u2010alkoxynitriles, \u03b1\u2010aminonitriles and \u03b1\u2010cyanohydrazones become easily available. These exhibit synthetically valuable substitution patterns for the synthesis of pharmaceuticals, intermediates for total synthesis and amino acid synthesis.<\/jats:p>","DOI":"10.1002\/anie.202309274","type":"journal-article","created":{"date-parts":[[2023,7,29]],"date-time":"2023-07-29T16:39:34Z","timestamp":1690648774000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":21,"title":["Light\u2010Induced Metal\u2010Free Generation of Cyanocarbenes from Alkynyl Triazenes for the Synthesis of Nitrile Derivatives"],"prefix":"10.1002","volume":"62","author":[{"given":"Elena","family":"Michel","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Organische Chemie Heidelberg University  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fabian F.","family":"Grieser","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Organische Chemie Heidelberg University  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alexandra V.","family":"Mackenroth","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Organische Chemie Heidelberg University  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Michael","family":"Schukin","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Organische Chemie Heidelberg University  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Petra","family":"Kr\u00e4mer","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Organische Chemie Heidelberg University  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shaista","family":"Tahir","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Organische Chemie Heidelberg University  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Frank","family":"Rominger","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Organische Chemie Heidelberg University  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Matthias","family":"Rudolph","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Organische Chemie Heidelberg University  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6720-8602","authenticated-orcid":false,"given":"A. 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