Behera Deepak, Schulte Tim, Altun Ahmet, Leutzsch Markus, Neese Frank, Ritter Tobias
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr 45470, Germany.
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany.
Org Lett. 2025 Aug 15;27(32):8921-8926. doi: 10.1021/acs.orglett.5c02410. Epub 2025 Aug 4.
Herein, we report a straightforward methodology for direct deaminative cyanation of anilines via aryl diazonium salts as fleeting intermediates. The approach leverages the kinetic stability of nitrate and copper cyanide, iron's ability to facilitate nitrate reduction, and appropriate relative rates to ensure the product-forming kinetic reaction pathway despite several thermodynamically favored, undesired reactions. We present insight into the previously unappreciated nitrate reduction mechanism by simple sulfur-based reductants, such as SO. The oxylanion radical transfer mechanism is rarely encountered in synthetic chemistry but has ample precedent in biology and could provide a general, useful strategy for chemical nitrate reduction.
在此，我们报道了一种直接的方法，通过芳基重氮盐作为瞬态中间体对苯胺进行直接脱氨基氰化反应。该方法利用了硝酸盐和氰化铜的动力学稳定性、铁促进硝酸盐还原的能力以及适当的相对速率，以确保尽管存在几种热力学上有利的不期望反应，但仍能形成产物的动力学反应途径。我们通过简单的硫基还原剂（如SO）对以前未被认识的硝酸盐还原机制进行了深入研究。氧阴离子自由基转移机制在合成化学中很少见，但在生物学中有充分的先例，并且可以为化学硝酸盐还原提供一种通用的、有用的策略。
