Iron-catalyzed selective reduction of nitro compounds to amines

In Situ Generated Iron Oxide Nanocrystals as Efficient and Selective Catalysts for the Reduction of Nitroarenes using a Continuous Flow Method

“…[1] While traditional non-catalytic reduction processes (that is using Fe/HCl) generate large amounts of undesirable waste; catalytic hydrogenation using heterogeneous transition-metal catalysts is a well-established technique and often the method of choice for the reduction of nitroarenes to anilines. Apart from the use of hydrogen, several other stoichiometric reducing agents such as ammonium salts, [5] silanes, [6] boranes, [7] sodium borohydride, [8] formic acid, [9] and hydrazine, [10] have been used in combination with a number of different metal catalysts. [3] Therefore, significant efforts have been made to develop more efficient and sustainable methods to achieve the selective reduction of nitroarenes to anilines.…”

“…[2,3] However, selectivity problems in the presence of other common functional groups can occur, [4] often requiring the use of carefully selected and expensive precious metal catalysts (for example, Pd, Pt, or Ru). [5][6][7][8][9][10] Hydrazine, specifically the less hazardous hydrazine hydrate (N 2 H 4 ·H 2 O), is a particularly good reagent because it generates only N 2 as a side product and is comparatively safe to handle. Apart from the use of hydrogen, several other stoichiometric reducing agents such as ammonium salts, [5] silanes, [6] boranes, [7] sodium borohydride, [8] formic acid, [9] and hydrazine, [10] have been used in combination with a number of different metal catalysts.…”

Amine synthesis via transition metal homogeneous catalysed hydrosilylation

“…of TMDS in THF at 60 °C for 24-48 h with similar group tolerance. 111 In 2015, Baran et al described an interesting sequence involving a nitroarene reduction following by a hydroamination of alkenes leading to the corresponding secondary amines. 112a Indeed, using 30 mol% of Fe(acac) 3 as the catalyst in the presence of 3 equiv.…”

Reduction of Aromatic and Aliphatic Esters Using the Reducing Systems MoO2(acac)2 or V(O)(OiPr)3 in Combination with 1,1,3,3‐Tetramethyldisiloxane

“…Since then, other molybdenum complexes have been employed for hydrosilylation. [36,37,38] In our laboratory, TMDS has already been employed to efficiently reduce a range of functions such as phosphane oxides, [39] nitriles, [40] amides, [41] nitro, [42] acetals, [43] and ketones [44] depending on the nature of the metal catalyst. We report herein a new method for the reduction of aromatic or aliphatic esters into alcohols using TMDS as reducing agent in association with two different metal sources to compare their reactivity.…”