126541-72-8Relevant academic research and scientific papers
General Synthesis of Secondary Alkylamines by Reductive Alkylation of Nitriles by Aldehydes and Ketones
Sch?nauer, Timon,Thom?, Sabrina L. J.,Kaiser, Leah,Zobel, Mirijam,Kempe, Rhett
supporting information, p. 1609 - 1614 (2020/12/22)
The development of C?N bond formation reactions is highly desirable due to their importance in biology and chemistry. Recent progress in 3d metal catalysis is indicative of unique selectivity patterns that may permit solving challenges of chemical synthesis. We report here on a catalytic C?N bond formation reaction—the reductive alkylation of nitriles. Aldehydes or ketones and nitriles, all abundantly available and low-cost starting materials, undergo a reductive coupling to form secondary alkylamines and inexpensive hydrogen is used as the reducing agent. The reaction has a very broad scope and many functional groups, including hydrogenation-sensitive examples, are tolerated. We developed a novel cobalt catalyst, which is nanostructured, reusable, and easy to handle. The key seems the earth-abundant metal in combination with a porous support material, N-doped SiC, synthesized from acrylonitrile and a commercially available polycarbosilane.
Osmium-Promoted Transformation of Alkyl Nitriles to Secondary Aliphatic Amines: Scope and Mechanism
Babón, Juan C.,Esteruelas, Miguel A.,López, Ana M.,O?ate, Enrique
supporting information, p. 2177 - 2188 (2020/06/08)
The transformation of alkyl nitriles to symmetrical and asymmetrical secondary aliphatic amines promoted by the hexahydride complex OsH6(PiPr3)2 (1) is described, and the mechanisms of the reactions involved are established. Complex 1 catalyzes the aforementioned transformations of aryl-, pyridyl-, and alkoxy-functionalized alkyl nitriles with linear or branched chains. The formation of the secondary amines involves primary imines, primary amines, and secondary imines as organic intermediates. The reactions take place under mild conditions (toluene, 100 °C, and 4 bar of H2). Stoichiometric reactions of 1 with pivalonitrile and 2-methoxyacetonitrile have allowed us to isolate the trihydride azavinylidene derivatives OsH3{═N═CHR}(PiPr3)2 (R = tBu (3), CH2OMe (4)). Their formation involves the insertion of the N-C triple bond of the substrates into an Os-H bond of the unsaturated tetrahydride OsH4(PiPr3)2 (A), which is generated by reductive elimination of H2 from the hexahydride precursor. The reaction of these trihydride azavinylidene species with H2 is the key step for the reduction of the N-C triple bond of the nitriles. In the absence of H2, the attack of A to the azavinylidene ligand produces the rupture of its C(sp2)-C(sp3) bond. As a consequence of this attack and the presence of primary imines and amines in the reaction media, the binuclear complexes (PiPr3)2H4Os(μ-CN)OsH3{κ1-N-(NH═CHCH2OMe)}(PiPr3)2 (5) and (PiPr3)2H4Os(μ-CN)OsH3{κ1-N-(NH2CH2CH2OMe)}(PiPr3)2 (6) have been isolated and characterized by X-ray diffraction analysis, for 2-methoxyacetonitrile. DFT calculations reveal noticeable similarities between the hydrogenations of nitriles to primary imines and those of primary imines to primary amines.
Catalytic C - H amination with unactivated amines through copper(II) amides
Wiese, Stefan,Badiei, Yosra M.,Gephart, Raymond T.,Mossin, Susanne,Varonka, Matthew S.,Melzer, Marie M.,Meyer, Karsten,Cundari, Thomas R.,Warren, Timothy H.
supporting information; experimental part, p. 8850 - 8855 (2011/02/24)
En route to catalysis: Two equivalents of the three-coordinate copper(II) amide [(Cl2NN)Cu]-NHAd participate in stoichiometric C - H amination by a H-atom abstraction/radical capture sequence. This active species may be generated through a copper(II) tert-butoxide intermediate to allow for the unprecedented catalytic amination of sp3-C - H bonds with unactivated alkylamines. This method greatly expands the range of amines for catalytic C - H amination since most protocols require N-based electron-withdrawing groups.
Radical cyclisations of imines and hydrazones
Bowman, W. Russell,Stephenson, Peter T.,Terrett, Nicholas K.,Young, Adrian R.
, p. 7959 - 7980 (2007/10/02)
Radical cyclisation of sp3 carbon-centred radicals onto imines and hydrazones provides a new method for the synthesis of 5- and 6-membered ring nitrogen heterocycles. Cyclisation onto the electrophilic carbon of the C=N group and 5-exo stereoelectronic selectivity are the dominating mechanistic parameters. The C-centred radical intermediates were generated from benzeneselenyl precursors using Bu3SnH.
The N-Substitution of Aliphatic Primary Amines via 1-benzotriazoles: Preparation of Secondary Amines
Katritzky, Alan R.,Glen, Noble,Pilarski, Boguslaw,Harris, Philip
, p. 1443 - 1446 (2007/10/02)
A new method has been developed for the selective conversion of primary aliphatic amines into unsymmetrical secondary amines by Grignard reaction of 1-benzotriazoles 1.This method employs simple procedures and mild conditions, and is specific in that onyl monoalkylation of the primary amines results.
