27126-93-8Relevant articles and documents
Hydrosilylative reduction of primary amides to primary amines catalyzed by a terminal [Ni-OH] complex
Bera, Jitendra K.,Pandey, Pragati
, p. 9204 - 9207 (2021/09/20)
A terminal [Ni-OH] complex1, supported by triflamide-functionalized NHC ligands, catalyzes the hydrosilylative reduction of a range of primary amides into primary amines in good to excellent yields under base-free conditions with key functional group tolerance. Catalyst1is also effective for the reduction of a variety of tertiary and secondary amides. In contrast to literature reports, the reactivity of1towards amide reduction follows an inverse trend,i.e., 1° amide > 3° amide > 2° amide. The reaction does not follow a usual dehydration pathway.
Catalytic Cyanation Using CO2 and NH3
Wang, Hua,Dong, Yanan,Zheng, Chaonan,Sandoval, Christian A.,Wang, Xue,Makha, Mohamed,Li, Yuehui
supporting information, p. 2883 - 2893 (2019/01/05)
Li and co-workers describe the catalytic cyanation of organic halides with CO2 and NH3. In the presence of Cu2O/DABCO as the catalyst, a variety of aromatic bromides and iodides were transformed to the desired nitrile products with broad functional-group tolerance. Both 13C- and/or 15N-labeled nitriles were obtained conveniently with appropriately isotope-labeled CO2 and NH3. Construction of functionalized chemical compounds from small molecules in a highly selective and efficient manner is crucial for sustainable development. The chemical-based manufacturing sector of the future should aim to produce chemicals from very simple and abundant resources, just as nature uses CO2 and N2 to generate sugars, amino acids, and so forth. In practice, however, the utilization of CO2 for the generation of industrial products, such as drugs and related intermediates, still remains a major challenge. Here, we describe the facile cyanide-free production of high-value nitriles with CO2 and NH3 as the sole sources of carbon and nitrogen, respectively. This practical and catalytic methodology provides a unique strategy for the utilization of small molecules for sustainable and cost-effective applications. Selective cyanation of aryl halides was achieved with CO2 and NH3 as the only sources of carbon and nitrogen, respectively. In the presence of Cu catalysts under low pressure (3 atm), a variety of aromatic iodides and bromides were transformed to the desired nitrile products without the use of toxic metal cyanides. Notably, olefins, esters, amides, alcohols, and amino groups were tolerated. Mechanistic studies suggest that Cu(III)-aryl insertion by isocyanate intermediates is involved. [13C,15N]-labeled nitriles were conveniently accessible from the respective isotope-labeled CO2 and NH3 via this methodology.
Metal-Free Oxidation of Primary Amines to Nitriles through Coupled Catalytic Cycles
Lambert, Kyle M.,Bobbitt, James M.,Eldirany, Sherif A.,Kissane, Liam E.,Sheridan, Rose K.,Stempel, Zachary D.,Sternberg, Francis H.,Bailey, William F.
supporting information, p. 5156 - 5159 (2016/04/09)
Synergism among several intertwined catalytic cycles allows for selective, room temperature oxidation of primary amines to the corresponding nitriles in 85-98 % isolated yield. This metal-free, scalable, operationally simple method employs a catalytic quantity of 4-acetamido-TEMPO (ACT; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide) radical and the inexpensive, environmentally benign triple salt oxone as the terminal oxidant under mild conditions. Simple filtration of the reaction mixture through silica gel affords pure nitrile products.
