- Hydroborative reduction of amides to amines mediated by La(CH2C6H4NMe2-: O)3
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The deoxygenative reduction of amides to amines is a great challenge for resonance-stabilized carboxamide moieties, although this synthetic strategy is an attractive approach to access the corresponding amines. La(CH2C6H4NMe2-o)3, a simple and easily accessible lanthanide complex, was found to be highly efficient not only for secondary and tertiary amide reduction, but also for the most challenging primary reduction with pinacolborane. This protocol exhibited good tolerance for many functional groups and heteroatoms, and could be applied to gram-scale synthesis. The active species in this catalytic cycle was likely a lanthanide hydride.
- Gong, Mingliang,Guo, Chenjun,Luo, Yunjie,Xie, Hongzhen,Zhang, Fangcao
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p. 779 - 791
(2022/01/22)
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- Iron-catalysed hydroboration of non-activated imines and nitriles: Kinetic and mechanistic studies
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Iron-catalysed hydroboration of imines and nitriles has been developed under low catalyst loading (1 mol%) in the presence of HBpin. A wide scope of substrate was found to smoothly undergo hydroboration, including electron releasing/withdrawing and haloge
- Bazkiaei, Adineh Rezaei,Wiseman, Michael,Findlater, Michael
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p. 15284 - 15289
(2021/05/19)
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- Lithium compound catalyzed deoxygenative hydroboration of primary, secondary and tertiary amides
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A selective and efficient route for the deoxygenative reduction of primary to tertiary amides to corresponding amines has been achieved with pinacolborane (HBpin) using simple and readily accessible 2,6-di-tert-butyl phenolate lithium·THF (1a) as a catalyst. Both experimental and DFT studies provide mechanistic insight. This journal is
- Bisai, Milan Kumar,Gour, Kritika,Das, Tamal,Vanka, Kumar,Sen, Sakya S.
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supporting information
p. 2354 - 2358
(2021/03/03)
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- La[N(sime3)2]3-catalyzed deoxygenative reduction of amides with pinacolborane. scope and mechanism
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Tris[N,N-bis(trimethylsilyl)amide]lanthanum (LaNTMS) is an efficient and selective homogeneous catalyst for the deoxygenative reduction of tertiary and secondary amides with pinacolborane (HBpin) at mild temperatures (25-60 °C). The reaction, which yields amines and O(Bpin)2, tolerates nitro, halide, and amino functional groups well, and this amide reduction is completely selective, with the exclusion of both competing inter- and intramolecular alkene/alkyne hydroboration. Kinetic studies indicate that amide reduction obeys an unusual mixed-order rate law which is proposed to originate from saturation of the catalyst complex with HBpin. Kinetic and thermodynamic studies, isotopic labeling, and DFT calculations using energetic span analysis suggest the role of a [(Me3Si)2N]2La-OCHR(NR′2)[HBpin] active catalyst, and hydride transfer is proposed to be ligand-centered. These results add to the growing list of transformations that commercially available LaNTMS is competent to catalyze, further underscoring the value and versatility of lanthanide complexes in homogeneous catalysis.
- Barger, Christopher J.,Dicken, Rachel D.,Weidner, Victoria L.,Motta, Alessandro,Lohr, Tracy L.,Marks, Tobin J.
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supporting information
p. 8019 - 8028
(2020/05/27)
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- In water alkylation of amines with alcohols through a borrowing hydrogen process catalysed by ruthenium nanoparticles
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A simple and environmentally benign procedure for the synthesis of secondary amines in water has been developed. Combining Ru3(CO)12, tetraphenylcyclopentadienone and a small quantity of TGPS-750-M surfactant, primary and secondary alcohols were alkylated at N employing equimolar amounts of aromatic amines in water. The reaction occurs under microwave (MW) dielectric heating with high conversion and high yield. When required, the use of biomass-derived 2-MeTHF or GVL as a co-solvent is possible. Under the influence of MWs, a Ru nanoparticle-nanomicelle combination was formed acting as an effective and recyclable catalyst. This protocol was also employed for "in water" cyclisation to synthesise biologically relevant pyrrolobenzodiazepines (PBDs).
- Risi, Caterina,Calamante, Massimo,Cini, Elena,Faltoni, Valentina,Petricci, Elena,Rosati, Filippo,Taddei, Maurizio
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supporting information
p. 327 - 331
(2020/02/13)
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- A Manganese Nanosheet: New Cluster Topology and Catalysis
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While the coordination chemistry of monometallic complexes and the surface characteristics of larger metal particles are well understood, preparations of molecular metallic nanoclusters remain a great challenge. Discrete planar metal clusters constitute nanoscale snapshots of cluster growth but are especially rare owing to the strong preference for three-dimensional structures and rapid aggregation or decomposition. A simple ligand-exchange procedure has led to the formation of a novel heteroleptic Mn6 nanocluster that crystallized in an unprecedented flat-chair topology and exhibited unique magnetic and catalytic properties. Magnetic susceptibility studies documented strong electronic communication between the manganese ions. Reductive activation of the molecular Mn6 cluster enabled catalytic hydrogenations of alkenes, alkynes, and imines.
- Chakraborty, Uttam,Reyes-Rodriguez, Efrain,Demeshko, Serhiy,Meyer, Franc,Jacobi von Wangelin, Axel
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supporting information
p. 4970 - 4975
(2018/03/28)
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- Copper-catalysed reductive amination of nitriles and organic-group reductions using dimethylamine borane
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A heterogeneous copper catalyst, formed in situ, has been shown to dehydrocouple commercially available amine boranes whilst transferring hydrogen for the reduction of selected organic functional groups in an aqueous medium. The catalytic system has also been shown to promote the reductive amination of aryl nitriles. This journal is
- Van Der Waals, Dominic,Pettman, Alan,Williams, Jonathan M. J.
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p. 51845 - 51849
(2014/12/10)
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- Diazepinoquinolines, synthesis thereof, and intermediates thereto
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The present invention relates to methods for synthesizing compounds useful as 5HT2C agonists or partial agonists, derivatives thereof, and to intermediates thereto.
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Page/Page column 12-13
(2008/06/13)
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- Contribution a l'evaluation de l'importance des facteurs electroniques et steriques gouvernant la reaction des boranes avec les azides
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Organoboranes react with azides to give, after hydrolysis, secondary amines.Scope and limitations of this method have been stated.When dibromoboranes were used, a competitive migration of the alkyl group and bromine leading to the simultaneous formation of a tetraazaboroline and the expected secondary amine was observed.A mechanism accounting for these results is proposed.
- Carboni, Bertrand,Vaultier, Michel,Courgeon, Thierry,Carrie, Robert
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p. 844 - 849
(2007/10/02)
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