Chiral N-phosphino sulfinamide ligands in rhodium(I)-catalyzed [2+2+2] cycloaddition reactions

Brun, Sandra; Parera, Magda; Pla‐Quintana, Anna; Roglans, Anna; León, Thierry; Achard, Thierry; Solà, Jordi; Verdaguer, Xavier; Riéra, Antoni

doi:10.1016/j.tet.2010.09.009

Cited by 40 publications

(30 citation statements)

References 76 publications

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“…General : Diynes 1 18 and 4 19 were prepared as previously described. Compounds 3 c 4j and 5 9g were prepared and characterized previously in our laboratory. Reaction mixtures were subjected to column chromatography on silica gel (230–400 mesh).…”

Section: Methodsmentioning

confidence: 99%

Direct Detection of Key Intermediates in Rhodium(I)‐Catalyzed [2+2+2] Cycloadditions of Alkynes by ESI‐MS

Parera

Dachs

Solà

et al. 2012

Chemistry A European J

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The mechanism of the Rh-catalysed [2+2+2] cycloaddition reaction of diynes with monoynes has been examined using ESI-MS and ESI-CID-MS analysis. The catalytic system used consisted of the combination of a cationic rhodium(I) complex with bisphosphine ligands, which generates highly active complexes that can be detected by ESI(+) experiments. ESI-MS on-line monitoring has allowed the detection for the first time of all of the intermediates in the catalytic cycle, supporting the mechanistic proposal based mainly on theoretical calculations. For all ESI-MS experiments, the structural assignments of ions are supported by tandem mass spectrometry analyses. Computer model studies based on density functional theory (DFT) support the structural proposal made for the monoyne insertion intermediate. The collective studies provide new insight into the reactivity of cationic rhodacyclopentadienes, which should facilitate the design of related rhodium-catalysed C-C couplings.

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Section: Methodsmentioning

confidence: 99%

Direct Detection of Key Intermediates in Rhodium(I)‐Catalyzed [2+2+2] Cycloadditions of Alkynes by ESI‐MS

Parera

Dachs

Solà

et al. 2012

Chemistry A European J

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“…5‐Hydroxymethylphthalan (13aa): 32 Colourless solid. 1 H NMR (300 MHz, CDCl 3 ): δ = 4.69 (s, 2 H, C H 2 OH), 5.09 (s, 5 H, C H 2 O + O H ), 7.19–7.27 (m, 3 H, C H ‐Ar) ppm.…”

Section: Methodsmentioning

confidence: 99%

“…5‐Phenyl‐2‐( p ‐tolylsulfonyl)‐1,3‐dihydroisoindole (13bb): 32 Colourless solid. 1 H NMR (300 MHz, CDCl 3 ): δ = 2.43 (s, 3 H, C H 3 ), 4.69 (br.…”

Section: Methodsmentioning

confidence: 99%

Rhodium‐NHC Hybrid Silica Materials as Recyclable Catalysts for [2+2+2] Cycloaddition Reactions of Alkynes

et al. 2014

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Bis-silylated dihydroimidazolium salt 1 and monosilylated imidazolium salt 2 are transformed to (NHC)RhCl(COD) complexes 3 and 4, which allow the preparation of hybrid silica materials either by sol-gel or grafting processes. After a full characterization of the materials by means of solid state NMR, N2-sorption measurements, thermogravimetric analysis (TGA) and elemental analysis, the catalytic activity is evaluated in the [2+2+2] cycloaddition of alkynes. Excellent yields of the cycloadducts are obtained for up to six consecutive cycles with the grafted material, using a simple filtration to recover the catalyst. Both conventional and microwave heating prove to be effective for the process described.

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“…[90] Reductive amination with aldehydes in the presence of a Lewis acid gave sulfinimines, which were reduced in situ to the corresponding sufinamides. [90] Reductive amination with aldehydes in the presence of a Lewis acid gave sulfinimines, which were reduced in situ to the corresponding sufinamides.…”

Section: Polydentate P/n P/o and P/olefin Ligandsmentioning

confidence: 99%

The Synthesis of Chiral Phosphorus Ligands for use in Homogeneous Metal Catalysis

2011

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Recent developments in the synthesis of chiral phosphorus ligands are summarized. Main emphasis is given to the multitude of protocols for their synthesis starting from compounds of the chiral pool or by using other easily available chiral starting materials. Besides mono-and bidentate P-ligands hybrid ligands bearing N, O, or olefinic groups as second ligating units are addressed. The syntheses of new P-chirogenic ligands, as well as ligands with supramolecular structures are likewise reviewed. In appropriate cases structures of related privileged ligands are given for comparison. When available, the efficiency of the new ligands for metal catalyzed reactions are briefly assessed.[a] Dr.

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Chiral N-phosphino sulfinamide ligands in rhodium(I)-catalyzed [2+2+2] cycloaddition reactions

Cited by 40 publications

References 76 publications

Direct Detection of Key Intermediates in Rhodium(I)‐Catalyzed [2+2+2] Cycloadditions of Alkynes by ESI‐MS

Direct Detection of Key Intermediates in Rhodium(I)‐Catalyzed [2+2+2] Cycloadditions of Alkynes by ESI‐MS

Rhodium‐NHC Hybrid Silica Materials as Recyclable Catalysts for [2+2+2] Cycloaddition Reactions of Alkynes

The Synthesis of Chiral Phosphorus Ligands for use in Homogeneous Metal Catalysis

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