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Rh-catalyzed hydroaminomethylation of 1-decene with diethylamine and possible side reactions observed: (A) hydroformylation yielding in branched aldehyde, (B) hydrogenation of aldehyde, (C) aldol reaction, (D) hydrogenation of 1-decene, and (E) isomerization of the double bond.
Source publication
The hydroaminomethylation of the long-chain olefin 1-decene and diethylamine with a homogeneous Rh(acac)(cod)/SulfoXantphos catalyst complex as a one-pot synthesis was investigated. The influence of reaction conditions such as temperature and synthesis gas pressure was determined, as well as the effects of the initial concentrations of catalyst pre...
Contexts in source publication
Context 1
... research group has set a focus on homogeneous catalysis in microemulsion systems. Therefore, we investigated the hydroaminomethylation of the long-chain olefin 1-decene with diethylamine, catalyzed by a water-soluble rhodium/phosphine catalyst complex (see Figure 1) and described the impact of reaction conditions on yields, selectivities and the effective reaction rate. Numerous side reactions can occur (reactions A-E) and must be avoided by choosing the optimum reaction conditions and concentrations of reactants. ...
Context 2
... shown in Figure 1, several side reactions can be observed aside from hydroaminomethylation. The aim is, of course, to suppress these as far as possible. ...
Citations
... Here, the reaction step is operated at 95 • C and 15 bar, while the phase separation is achieved in a subsequent settler unit, operated at 74-98 • C depending on current reaction yield and microemulsion configuration. The same principle has been successfully demonstrated for the reductive amination of undecanal [77] and the hydroaminomethylation of decene [78]. ...
Many years ago, twelve principles were defined for carrying out chemical reactions and processes from a green chemistry perspective. It is everyone’s endeavor to take these points into account as far as possible when developing new processes or improving existing ones. Especially in the field of organic synthesis, a new area of research has thus been established: micellar catalysis. This review article addresses the question of whether micellar catalysis is green chemistry by applying the twelve principles to micellar reaction media. The review shows that many reactions can be transferred from an organic solvent to a micellar medium, but that the surfactant also has a crucial role as a solubilizer. Thus, the reactions can be carried out in a much more environmentally friendly manner and with less risk. Moreover, surfactants are being reformulated in their design, synthesis, and degradation to add extra advantages to micellar catalysis to match all the twelve principles of green chemistry.
... Rh-catalyzed HAM has been recently used for the synthesis of indoles or indoline-2-ols, [13] gamma-aminobutyric esters, [14] beta-aminoesters [15] in homogeneous catalysis. Also, in several recent studies the catalyst was supported on an immiscible liquid phase [16][17][18][19] or on polymers [20,21] to facilitate the recycling. The use of an additional catalyst for the reductive amination step allowed for a drastic reduction on the temperature and syngas pressure. ...
2‐Arylpropylamines are useful as active pharmaceutical ingredients (APIs) and as synthetic building blocks in fine chemistry. Herein we report a new and efficient methodology to transform naturally occurring 1‐propenylbenzenes into 2‐arylpropylamines employing a one‐pot ethenolysis/hydroaminomethylation protocol. Four consecutive reactions must occur in the same reaction vessel and the careful selection of the reaction conditions was critical to obtain the desired products in high yields. The negative interference between the ethenolysis and the hydroaminomethylation (HAM) catalysts was circumvented by the appropriate adjustment on the molar ratio of the catalysts. As a result, nine 2‐arylpropylamines were obtained in yields ranging in 75–93 %.
... Due to the further development of more efficient cobalt and rhodium catalysts and the introduction of phosphorus ligands, HAM has become a powerful method for the synthesis of amines. [4][5][6][7][8][9][10][11][12][13][14][15] As HAM is a tandem catalytic process in which various catalytic cycles occur simultaneously, the conditions can be good for one catalytic cycle and deleterious for the other. For this reason, care in the choice of appropriate conditions is critical for the successful reaction sequence. ...
Hydroaminomethylation (HAM) is a tandem catalytic process that allows accessing amines from olefin scaffolds and is perfectly aligned with green chemistry precepts. In this work, HAM was applied to the natural hydroxyolefins: isoprenol, linalool, nerolidol, and isopulegol. Employing 4‐methylpiperidine, morpholine, and 1,2,3,4‐tetrahydroisoquinoline as counterparts, several new, structurally complex amines were prepared from biorenewable, low‐cost substrates, opening a path to exploit this structure diversity in biological activity. By the appropriate choice of rhodium‐based catalytic systems, as well as the reaction conditions, the necessary fine tuning for each counterpart was achieved. The unpromoted rhodium system leaded mostly to aminoalcohols, while certain phosphorus(III)‐promoted rhodium systems afforded amines containing a tetrahydropyran or a tetrahydrofuran moiety in moderate to high yields.
