86-53-3Relevant articles and documents
Ligand properties of aromatic azines: C-H activation, metal induced disproportionation and catalytic C-C coupling reactions
D?nnecke, Daniel,Wunderle, Joachim,Imhof, Wolfgang
, p. 585 - 594 (2004)
The reaction of aromatic azines with Fe2(CO)9 yields dinuclear iron carbonyl cluster compounds as the main products. The formation of these compounds may be rationalized by a C-H activation reaction at the aromatic substituent in ortho position with respect to the exocyclic C-N double bond followed by an intramolecular shift of the corresponding hydrogen atom toward the former imine carbon atom. The second imine function of the ligand does not react. Additional products arise from the metal induced disproportionation of the azine into a primary imine and a nitrile. So also one of the imine C-H bonds may be activated during the reaction. Depending on the aromatic substituent of the azine ligands iron carbonyl complexes of the disproportionation products are isolated and characterized by X-ray crystallography. C-C coupling reactions catalyzed by Ru3(CO)12 result in the formation of ortho-substituted azines. In addition, ortho-substituted nitriles are identified as side-products showing that the metal induced disproportionation reaction also takes place under catalytic conditions.
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McRae
, p. 4550 (1930)
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Cyanide-Free Cyanation of sp2 and sp-Carbon Atoms by an Oxazole-Based Masked CN Source Using Flow Microreactors
Sharma, Brijesh M.,Nikam, Arun V.,Lahore, Santosh,Ahn, Gwang-Noh,Kim, Dong-Pyo
supporting information, (2022/02/25)
This work reports a cyanide-free continuous-flow process for cyanation of sp2 and sp carbons to synthesize aryl, vinyl and acetylenic nitriles from (5-methyl-2-phenyloxazol-4-yl) boronic acid [OxBA] reagent as a sole source of carbon-bound mask
Visible-Light-Promoted Metal-Free Synthesis of (Hetero)Aromatic Nitriles from C(sp3)?H Bonds**
Murugesan, Kathiravan,Donabauer, Karsten,K?nig, Burkhard
supporting information, p. 2439 - 2445 (2020/12/07)
The metal-free activation of C(sp3)?H bonds to value-added products is of paramount importance in organic synthesis. We report the use of the commercially available organic dye 2,4,6-triphenylpyrylium tetrafluoroborate (TPP) for the conversion of methylarenes to the corresponding aryl nitriles via a photocatalytic process. Applying this methodology, a variety of cyanobenzenes have been synthesized in good to excellent yield under metal- and cyanide-free conditions. We demonstrate the scope of the method with over 50 examples including late-stage functionalization of drug molecules (celecoxib) and complex structures such as l-menthol, amino acids, and cholesterol derivatives. Furthermore, the presented synthetic protocol is applicable for gram-scale reactions. In addition to methylarenes, selected examples for the cyanation of aldehydes, alcohols and oximes are demonstrated as well. Detailed mechanistic investigations have been carried out using time-resolved luminescence quenching studies, control experiments, and NMR spectroscopy as well as kinetic studies, all supporting the proposed catalytic cycle.
