Selective hydroaminomethylation of olefins using simple and efficient Rh–phosphinite complex catalyst

Khan, Shoeb R.; Bhanage, Bhalchandra M.

doi:10.1002/aoc.3046

Cited by 18 publications

(4 citation statements)

References 31 publications

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“…With 100 mg of Rh 1 /TiO 2 , the main products of hydroaminoalkylation of 3.0 mmol of 1‐hexene and 3.0 mmol of 1‐piperidine are the branched product, 1‐(2‐methylhexyl)piperidine and linear product, 1‐heptylpiperidine clearly observed at t =4.88 min and t =5.29 min, respectively (Figure 3b). The identities of the two products were confirmed by comparing their mass spectra (Figure 3c and d) to these mass spectra of linear and branched products reported in literatures [25, 26] . Under the catalytic condition described in caption of Figure 3, the conversion of 1‐piperidine in the hydroaminoalkylation of 1‐hexene at 110 °C for 12 hrs is 78 % (Entry 1 in Table 1).…”

Section: Resultssupporting

confidence: 61%

“…The identities of the two products were confirmed by comparing their mass spectra (Figure 3c and d) to these mass spectra of linear and branched products reported in literatures. [25,26] Under the catalytic condition described in caption of Figure 3, the conversion of 1-piperidine in the hydroaminoalkylation of 1-hexene at 110 °C for 12 hrs is 78 % (Entry 1 in Table 1). Selectivity for linear and branched products are 98 %.…”

Section: Resultsmentioning

confidence: 99%

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C−N Coupling through Hydroaminoalkylation on a Single‐Atom Rh Heterogeneous Catalyst

Tang

Tao

2023

Angewandte Chemie

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C−N coupling is significant for the synthesis of fine chemicals toward various applications. Hydroaminoalkylation of olefins is a tandem reaction of C−N coupling involving first the formation of an aldehyde through hydroformylation of an olefin and then the production of amine through reductive amination of the aldehyde. Here we report a stable, supported catalyst of singly dispersed Rh1 atoms anchored on TiO2 (P25) nanoparticles designated as Rh1/P25. Its high activity for C−N coupling was demonstrated by six hydroaminoalkylations of olefins and amines with selectivity of higher than 90% for producing tertiary amines. The singly dispersed Rh1O4 on P25 exhibit activity and selectivity for hydroaminoalkylation comparable or even higher than some reported molecular catalysts. In contrast to molecular catalysts, the Rh‐based single‐atom Rh heterogeneous catalysis (Rh1/P25) can be readily separated from reactants and products, reused for multiple runs of hydroaminoalkylation, and recycled with a low cost.

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Section: Resultssupporting

confidence: 61%

Section: Resultsmentioning

confidence: 99%

C−N Coupling through Hydroaminoalkylation on a Single‐Atom Rh Heterogeneous Catalyst

Tang

Tao

2023

Angewandte Chemie

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“…The hydroaminomethylation of alkenes is a cascade reaction of two consecutive reactions. [74][75][76][77] The alkene substrate first undergoes a hydroformylation reaction 32 to form an aldehyde and then the reductive amination of the resulting aldehyde with an amine produces an N-alkylated amine (Scheme 3). [34][35][36][37]78 Despite the fact that the hydroaminomethylation reaction was originally discovered by Reppe in the early 1950s at BASF using Fe(CO) 5 in nearly stoichiometric amounts, 79,80 intensive research on this topic only started in the past fifteen years.…”

Section: Hydroaminomethylation Of Alkenesmentioning

confidence: 99%

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

Raoufmoghaddam

2014

Org. Biomol. Chem.

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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.

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“…The most attractive feature of this catalytic system lies in the mild pressure and temperature conditions used ( p CO / p H2 = 5:25 bar; 60 °C) since maintaining a low temperature is particularly important to favor the branched amine. This high regioselectivity was also observed with [Rh 2 Cl 2 (μ-diphosphinite)(COD) 2 ] (Scheme ) for styrene and dipentylamine ( l / b = 9:91) …”

Section: Mechanism and Selectivitymentioning

confidence: 99%

Tandem Hydroaminomethylation Reaction to Synthesize Amines from Alkenes

2018

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In the context of atom economy and low environmental impact, synthesis of amines by an efficient catalytic process is of great importance to produce these building blocks for fine chemical industry. The one-pot hydroaminomethylation of alkenes is a tandem reaction which involves three successive steps under CO/H pressure to perform the catalyzed hydroformylation of the alkene into the corresponding aldehyde followed by its condensation with a N-H function and the catalyzed hydrogenation of the imine/enamine intermediate into the corresponding saturated amine. Rhodium and more recently ruthenium complexes have been designed to combine high conversions of the reactants and chemoselectivity in the expected amines with high regioselectivity in either the linear or the branched amine. The coordination sphere of the metal according to the presence of ligands, temperature, CO/H partial pressures, and nature of the solvent is essential for complying with these selectivity requirements. The rate of the hydroformylation step needs to be fast with regard to the hydrogenation step. The role of amines in the coordination sphere and water, presumably in the second sphere, on the mechanism requires some more studies. Similarly, the enantioselective synthesis of amine is not yet achieved directly and interrupted processes or use of asymmetric organo-catalyzed reductive amination are efficient synthetic ways for producing chiral amines. The separation of the catalyst from the organic products by biphasic or (semi-) heterogeneized systems and its recycling have been demonstrated in many cases. The present review provides a report of the state of the art in this autotandem hydroaminomethylation catalysis and should open prospects in the design of less expensive and abundant metal complexes for reaching at low cost similar and even superior performances.

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Selective hydroaminomethylation of olefins using simple and efficient Rh–phosphinite complex catalyst

Cited by 18 publications

References 31 publications

C−N Coupling through Hydroaminoalkylation on a Single‐Atom Rh Heterogeneous Catalyst

C−N Coupling through Hydroaminoalkylation on a Single‐Atom Rh Heterogeneous Catalyst

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

Tandem Hydroaminomethylation Reaction to Synthesize Amines from Alkenes

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