Selective Synthesis of N‐Alkyl Hydroxylamines by Hydrogenation of Nitroalkanes using Supported Palladium Catalysts

An Efficient Continuous Flow Synthesis for the Preparation of N-Arylhydroxylamines: Via a DMAP-Mediated Hydrogenation Process

“…The electron-donating group ( 9a , 10a ) could enrich the electrons of -NHOH, leading to the tendency of -NHOH to adsorb on the catalyst surface and convert to -NH 2 . The steric effect depends on the positions of the substituents [ 17 , 41 ]. In the cases of chloronitrobenzene ( 1a – 3a ) hydrogenation, 1a and 1b have the largest steric hindrance, while that of 3a and 3b are the opposite.…”

“…N -Arylhydroxylamines ( N -AHA) are versatile organic molecules used as intermediates to synthesize industrially valuable fine chemicals, bioactive drugs, and polymerization inhibitors [ 1 , 2 , 3 , 4 , 5 , 6 ]. Among the reported protocols for obtaining N -AHA, the selective reduction of nitroarenes is the most convenient, which involves a biocatalytic reduction by baker’s yeast or plant cell [ 7 , 8 ], the use of Fe or Zn in stoichiometric quantity [ 9 , 10 , 11 ], and homogeneous or heterogeneous metal catalysts (with Pt, Ni, Pd, Rh, Ir, Ag, Au) with hydrazine or H 2 [ 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 ]. At present, lots of attention is focused on the development of a heterogeneous metal catalytic system because of its great stability, reusability, and easy isolation.…”

Synthesis of a Crizotinib Intermediate via Highly Efficient Catalytic Hydrogenation in Continuous Flow

“…In general, the catalytic hydrogenation of aromatic nitro compounds containing functional groups, such as halogens, benzyl, and so on, with high selectivity (≥99%) is one of the challenges. According to the reports, the results can be divided into two categories based on the class of catalysts: adopting precious metal catalysts and using novel catalysts with yields in the range of 63–100%. − However, the batch process for catalytic hydrogenation has some safety issues, such as normally tedious postprocessing and poor controllability of product dynamics.…”

O2‐Mediated Oxidation of Aminoboranes through 1,2‐N Migration

“…[5] Commonly,they are prepared through radical one-step addition of DBPO to the corresponding amine. [7] Orthogonal approaches are based on the reduction of either nitro [8] or oxime [9] moieties to generate primary hydroxylamines.T he direct reductive alkylation of aliphatic nitro compounds via nitroso intermediates remains challenging. [7] Orthogonal approaches are based on the reduction of either nitro [8] or oxime [9] moieties to generate primary hydroxylamines.T he direct reductive alkylation of aliphatic nitro compounds via nitroso intermediates remains challenging.…”