Recent advances in catalytic C–N bond formation: a comparison of cascade hydroaminomethylation and reductive amination reactions with the corresponding hydroamidomethylation and reductive amidation reactions

Abstract

The design and catalytic implementation of tandem reactions to selectively create nitrogen-containing products under mild conditions has encountered numerous challenges in synthetic chemistry. Several known classes of homogeneously catalyzed carbon-nitrogen bond formation including hydroamination, hydroamidation, hydroaminoalkylation, hydroaminomethylation and reductive amination were reported in the literature. More recently, a new class of C-N bond formation consisting of hydroamidomethylation and reductive amidation extended the applicability of these synthetic methodologies. The tandem reactions do considerably impact on the selectivity and efficiency of synthetic strategies. This review highlights and compares selected examples of the hydroaminomethylation, reductive amination, hydroamidomethylation and reductive amidation reactions, and thus consequently reveals their potential applications in synthetic chemistry as well as chemical industries.

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

“…Transition metal catalyzed tandem catalyses often involve hydroformylation as the initial reaction step to form reactive aldehydes [14], which constitutes a well investigated reaction that is also the subject ongoing research [15][16][17]. Hydroformylation is an important part of the hydroaminomethylation, which is a three step autotandem catalysis catalyzed by a single catalyst [16,[18][19][20][21][22][23][24]. Past investigations have applied different renewables [25][26][27][28][29][30] in the hydroaminomethylation reaction to increase the sustainability of the overall reaction sequence.…”

Carbon Dioxide Transformation in Imidazolium Salts: Hydroaminomethylation Catalyzed by Ru‐Complexes

“…[43] Furthermore, in general, the main drawback of the hydroaminomethylation reactioni st hat for primary amines the selectivity generally is low because of over-alkylation. [44] Our catalytic system provided the formation of secondary amines from primary amines (2a and 2b)w ith no formation of over-alkylated amine. Thiss electivity is proba-Scheme2.Abnormal NHC carbenes possibly formedi nt he reaction of [BMI]Cl and [BMMI]Clw ith Ru 3 (CO) 12 under hydroformylation conditionsu sing CO 2 as aC Os ource.…”

“…Furthermore, the reaction of benzaldehydeand amines under the same reactionconditions affords the expected hydroaminomethylation product (Scheme7)similar to other complexes reported in the literature. [44] Hence the reductivea minationo fa ldehydes and ketones probably occurs under hydroaminomethylation conditions. The possible involvement of amides in the reaction mechanism can be in principle discarded as no catalytic activity for the reduction of amide (14 was used as am odel amide, Scheme 8) was observed.…”

Rhodium-catalyzed hydroaminomethylation of cyclopentadiene

“…3,4 Various amines can be synthesized in a simple, efficient and atom-economic way by performing a hydroaminomethylation reaction (HAM). [10][11][12][13][14][15][16][17] Highlights of the recent advantages are applications on natural products, 18 direct synthesis of drugs [19][20][21] and monomers for plastics, 22 isomerization and hydroaminomethylation of internal olens to linear amines, 23,24 catalyst recycling approaches by immobilization 25,26 or two-phase techniques 27,28 and mechanistic insights. In the rst step, a hydroformylation of an olen is performed followed by the condensation of the resulting aldehyde with a primary or secondary amine to give the corresponding enamine or imine with water as a byproduct.…”