Samarium diiodide/nickel diiodide an efficient system for homo and heterocoupling reactions of imines

Machrouhi, Fouzia; Namy, Jean‐Louis

doi:10.1016/s0040-4039(98)02673-2

Cited by 100 publications

(30 citation statements)

References 16 publications

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“…The iminebenzylidenephenylamine does not react with SmI 2 in the absence of additives at room temperature. During reflux in THF the imino–pinacol coupling is completed in 30 minutes (Scheme );33, 34 the addition of MeOH at room temperature does not give reduction of the imine to the corresponding amine, as would be expected, instead smaller amounts of imino–pinacol product were obtained. However, the SmI 2 /H 2 O/TMEDA mixture resulted in primarily imino–pinacol product (>90 %) and smaller amounts of the reduced imine, when water was slowly added to SmI 2 subsequent to amine and imine (determined by 1 H and 13 C NMR spectroscopy).…”

Section: Resultsmentioning

confidence: 82%

Instantaneous SmI₂/H₂O/Amine‐Mediated Reductions in THF

Dahlén

Hilmersson

2003

Chemistry A European J

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The SmI(2)-mediated reductions of ketones, imines, and alpha,beta-unsaturated esters have been shown to be instantaneous in the presence of H(2)O and an amine in THF. The SmI(2)-mediated reductions are not only shown to be fast and quantitative by the addition of H(2)O and an amine, but the workup procedures are also simplified. Competing experiments with SmI(2)/H(2)O/amine confirmed that alpha,beta-unsaturated esters could be selectively reduced in the presence of ketones or imines. Comparison of analogue ligands showed that nitrogen and phosphorus ligands are superior to oxygen and sulfur ligands in these reductions. The trialkylphosphine 1,2-bis(dimethylphosphino)ethane (DMPE) provided a primary kinetic isotope effect, yielding a k(H)/k(D) of 4.5.

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Section: Resultsmentioning

confidence: 82%

Instantaneous SmI₂/H₂O/Amine‐Mediated Reductions in THF

Dahlén

Hilmersson

2003

Chemistry A European J

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“…Next, the homocoupling reactions of substituted (E)-N-benzylidene-[1,1'-biphenyl]-2-amines were studied in CH 3 OH (Scheme 3) [51][52][53][54][55][56]. It is noteworthy that the resulting symmetrical 1,2-diamine compounds are potential ligands for a variety of organic transformations.…”

Section: Resultsmentioning

confidence: 99%

Distinctive reactivity of N-benzylidene-[1,1'-biphenyl]-2-amines under photoredox conditions

Tambe

Min

Iqbal

et al. 2020

Beilstein J. Org. Chem.

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A simple photocatalytic method was developed for the synthesis of unsymmetrical 1,2-diamines by the unprecedented reductive coupling of N-benzylidene-[1,1'-biphenyl]-2-amines with an aliphatic amine. The presence of a phenyl substituent in the aniline moiety of the substrate was critical for the reactivity. The reaction proceeded via radical–radical cross-coupling of α-amino radicals generated by proton-coupled single-electron transfer in the presence of an Ir photocatalyst. On the other hand, symmetrical 1,2-diamines were selectively produced from the same starting materials by the judicious choice of the reaction conditions, showcasing the distinct reactivity of N-benzylidene-[1,1'-biphenyl]-2-amines. The developed method can be employed for the synthesis of various bulky vicinal diamines, which are potential ligands in stereoselective synthesis.

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“…In addition, hetero couplings between ketones and imines are obtained in high yields by the SmI 2 / NiI 2 mixture within five minutes. [47] However, the details regarding the high reactivity of this catalytic system is not yet available preventing full utilisation of this interesting additive.…”

Section: Addition Of Metal Salts and Other Counterionsmentioning

confidence: 99%

Samarium(II) Iodide Mediated Reductions − Influence of Various Additives

2004

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Samarium(II) iodide is a one‐electron transfer reagent that has become highly appreciated as a mild and selective reducing agent in recent years. It has been found experimentally that various additives and co‐solvents largely control the reactivity of SmI2. This microreview provides an overview of the current knowledge of the reagent SmI2 as a reducing agent, in particular with additives that increase its reactivity. The use of various proton sources is covered, as well as the effect of co‐solvents. Furthermore, the very powerful reagent mixture SmI2/H2O/amine is also described. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Samarium diiodide/nickel diiodide an efficient system for homo and heterocoupling reactions of imines

Cited by 100 publications

References 16 publications

Instantaneous SmI₂/H₂O/Amine‐Mediated Reductions in THF

Instantaneous SmI₂/H₂O/Amine‐Mediated Reductions in THF

Distinctive reactivity of N-benzylidene-[1,1'-biphenyl]-2-amines under photoredox conditions

Samarium(II) Iodide Mediated Reductions − Influence of Various Additives

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Samarium diiodide/nickel diiodide an efficient system for homo and heterocoupling reactions of imines

Cited by 100 publications

References 16 publications

Instantaneous SmI2/H2O/Amine‐Mediated Reductions in THF

Instantaneous SmI2/H2O/Amine‐Mediated Reductions in THF

Distinctive reactivity of N-benzylidene-[1,1'-biphenyl]-2-amines under photoredox conditions

Samarium(II) Iodide Mediated Reductions − Influence of Various Additives

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Instantaneous SmI₂/H₂O/Amine‐Mediated Reductions in THF

Instantaneous SmI₂/H₂O/Amine‐Mediated Reductions in THF