51964-30-8Relevant articles and documents
Selective Catalytic Hydrogenations of Nitriles, Ketones, and Aldehydes by Well-Defined Manganese Pincer Complexes
Elangovan, Saravanakumar,Topf, Christoph,Fischer, Steffen,Jiao, Haijun,Spannenberg, Anke,Baumann, Wolfgang,Ludwig, Ralf,Junge, Kathrin,Beller, Matthias
, p. 8809 - 8814 (2016)
Hydrogenations constitute fundamental processes in organic chemistry and allow for atom-efficient and clean functional group transformations. In fact, the selective reduction of nitriles, ketones, and aldehydes with molecular hydrogen permits access to a green synthesis of valuable amines and alcohols. Despite more than a century of developments in homogeneous and heterogeneous catalysis, efforts toward the creation of new useful and broadly applicable catalyst systems are ongoing. Recently, Earth-abundant metals have attracted significant interest in this area. In the present study, we describe for the first time specific molecular-defined manganese complexes that allow for the hydrogenation of various polar functional groups. Under optimal conditions, we achieve good functional group tolerance, and industrially important substrates, e.g., for the flavor and fragrance industry, are selectively reduced.
Understanding the binding properties of phosphorylated glycoluril-derived molecular tweezers and selective nanomolar binding of natural polyamines in aqueous solution
Heilmann, Michael,Knezevic, Melina,Piccini, Giovannimaria,Tiefenbacher, Konrad
supporting information, p. 3628 - 3633 (2021/05/04)
A modular synthetic platform for the construction of flexible glycoluril-derived molecular tweezers was developed. The binding properties of four exemplary supramolecular hosts obtained via this approach towards 16 organic amines were investigated by means of 1H NMR titration. In this work, we compare the Ka values obtained this way with those of three structurally related molecular tweezers and provide a computational approach towards an explanation of the observed behavior of those novel hosts. The results showcase that certain structural modifications lead to very potent and selective binders of natural polyamines, with observed binding of spermine below 10 nM. This journal is
Non-Pincer Mn(I) Organometallics for the Selective Catalytic Hydrogenation of Nitriles to Primary Amines
Gardu?o, Jorge A.,García, Juventino J.
, p. 392 - 401 (2019/01/11)
We report herein selective catalytic hydrogenation of nitriles to primary amines with the use of the non-pincer Mn(I) compound fac-[(CO)3Mn{iPr2P(CH2)2PiPr2}(OTf)] (2) as a catalytic precursor (3 mol %) in the presence of KOtBu (10 mol %) and 2-BuOH as solvent. Benchmark benzonitrile and electron-rich aromatic and aliphatic nitriles were hydrogenated under rather mild conditions (7 bar, 90 °C, 15 min) to produce the corresponding amines in excellent to very good isolated yields (83-97%, six examples). Increasing the H2 pressure and time (35 bar, 30 min) allowed for the production of (di)amines in excellent yields (94-98%, three examples) from electron-deficient aromatic nitriles and terephthalonitrile. Notably, adiponitrile was reduced to hexamethylenediamine in 53% isolated yield. Finally, mechanistic insights were performed and suggested unsaturated Mn-hydride species performing the elementary steps during catalytic turnover.
