2492-83-3Relevant articles and documents
Phosphine-Free Manganese Catalyst Enables Selective Transfer Hydrogenation of Nitriles to Primary and Secondary Amines Using Ammonia-Borane
Sarkar, Koushik,Das, Kuhali,Kundu, Abhishek,Adhikari, Debashis,Maji, Biplab
, p. 2786 - 2794 (2021/03/03)
Herein we report the synthesis of primary and secondary amines by nitrile hydrogenation, employing a borrowing hydrogenation strategy. A class of phosphine-free manganese(I) complexes bearing sulfur side arms catalyzed the reaction under mild reaction conditions, where ammonia-borane is used as the source of hydrogen. The synthetic protocol is chemodivergent, as the final product is either primary or secondary amine, which can be controlled by changing the catalyst structure and the polarity of the reaction medium. The significant advantage of this method is that the protocol operates without externally added base or other additives as well as obviates the use of high-pressure dihydrogen gas required for other nitrile hydrogenation reactions. Utilizing this method, a wide variety of primary and symmetric and asymmetric secondary amines were synthesized in high yields. A mechanistic study involving kinetic experiments and high-level DFT computations revealed that both outer-sphere dehydrogenation and inner-sphere hydrogenation were predominantly operative in the catalytic cycle.
Visible Light-Mediated Decarboxylation Rearrangement Cascade of Aryl- N-(acyloxy)phthalimides
Faderl, Christian,Budde, Simon,Kachkovskyi, Georgiy,Rackl, Daniel,Reiser, Oliver
, p. 12192 - 12206 (2018/09/21)
A Smiles-type radical rearrangement induced by visible-light-mediated decarboxylation of w-aryl-N-(acyloxy)phthalimides was developed, giving rise to pharmacologically important substance classes: phenylethylamine derivatives, dihydroisoquinolinones, and
Hydrogenation of Nitriles and Ketones Catalyzed by an Air-Stable Bisphosphine Mn(I) Complex
Weber, Stefan,St?ger, Berthold,Kirchner, Karl
supporting information, p. 7212 - 7215 (2018/11/25)
Efficient hydrogenations of nitriles and ketones with molecular hydrogen catalyzed by a well-defined bench-stable bisphosphine Mn(I) complex are described. These reactions are environmentally benign and atomically economic, implementing an inexpensive, earth-abundant nonprecious metal catalyst. A range of aromatic and aliphatic nitriles and ketones were efficiently converted into primary amines and alcohols, respectively, in good to excellent yields. The hydrogenation of nitriles proceeds at 100 °C with catalyst loading of 2 mol % and 20 mol % base (t-BuOK), while the hydrogenation of ketones takes place already at 50 °C, with a catalyst loading of 1 mol % and 5 mol % of base. In both cases, a hydrogen pressure of 50 bar was applied.
Novel Borane-Selenium Complex: Highly Selective Reduction of Tertiary Amides and Nitriles to the Corresponding Amines with Sodium Borohydride-Dialkylselenium Dibromide
Akabori, Sadatoshi,Takanohashi, Yoshinori
, p. 479 - 482 (2007/10/02)
The reaction of sodium borohydride with bis(2-bromoethyl)selenium dibromide and/or diethylselenium dibromide in tetrahydrofuran (THF) gave borane.Treatment of tertiary amides with mixtures of sodium borohydride and either of the dibromides in THF gave the corresponding amines.Similar reactions with secondary and primary amides did not proceed.Furthermore, under similar reduction conditions, the reaction of nitriles with the above reagents also gave the corresponding primary amines.