Electronic and steric effects of ligands as control elements for rhodium-catalyzed asymmetric hydrogenation

Gergely, Ildiko; Hegedűs, Csaba; Szöllősy, Áron; Monsees, Axel; Riermeier, Thomas H.; Bakos, József

doi:10.1016/j.tetlet.2003.09.217

Cited by 17 publications

(8 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Bakos and co-workers have applied new and previously prepared BINOL-and H 8 -BINOL-related phosphites 24 and 25 to Rh-catalysed asymmetric hydrogenation of alkenes [14,15].…”

Section: Phosphites and Phosphoramiditesmentioning

confidence: 99%

Substituent electronic effects in chiral ligands for asymmetric catalysis

Flanagan

Guiry

2006

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

“…Bakos and co-workers have applied new and previously prepared BINOL-and H 8 -BINOL-related phosphites 24 and 25 to Rh-catalysed asymmetric hydrogenation of alkenes [14,15].…”

Section: Phosphites and Phosphoramiditesmentioning

confidence: 99%

Substituent electronic effects in chiral ligands for asymmetric catalysis

Flanagan

Guiry

2006

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

“…The deployment of chiral phosphinite ligands is well established in transition metal catalysed asymmetric hydrogenation reactions, and usually these ligands take the form of bidentate diphosphinite donors. 5,7,[9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] We have demonstrated previously that two of the hydroxyl groups in chiro-inositols can be selectively converted into phosphinite donors with ease and the resulting bidentate diphosphinite chiral ligands can be successfully used in catalytic asymmetric hydrogenation reactions. 16,22,24 Since recent studies have revealed that monodentate ligands can be important and successful components in asymmetric catalysis we chose to prepare some related monophosphinite ligands that are also constructed from chiro-inositol scaffolds.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium and osmium complexes of hemilabile chiral monophosphinite ligands derived from 1D-pinitol or 1D-chiro-inositol as catalysts for asymmetric hydrogenation reactions

Slade

Lensink²,

Falshaw³

et al. 2014

Dalton Trans.

View full text Add to dashboard Cite

The monophosphinite ligands, 1D-1,2;5,6-di-O-cyclopentylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P1), 1D-1,2;5,6-di-O-isopropylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P2), 1D-1,2;5,6-di-O-cyclohexylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P3), and 1D-1,2;5,6-di-O-cyclopentylidene-3-O-ethyl-4-O-diphenylphosphino-chiro-inositol (D-P4), can be conveniently prepared from the chiral natural products 1D-pinitol or 1D-chiro-inositol. On treatment of toluene solutions of RuCl2(PPh3)3 with two mole equivalents of the ligands D-PY (Y = 1-4) the complexes RuCl2(D-P1)2 (1), RuCl2(D-P2)2 (4), RuCl2(D-P3)2 (5), or RuCl2(D-P4)2 (6), respectively, are formed. Similarly, treatment of OsCl2(PPh3)3 with D-P1 gives OsCl2(D-P1)2 (7). The single crystal X-ray structure determination of 1 reveals that each D-P1 ligand coordinates to ruthenium through phosphorus and the oxygen atom of the methoxyl group. Treatment of 1 with excess LiBr or LiI results in metathesis of the chloride ligands and RuBr2(D-P1)2 (2) or RuI2(D-P1)2 (3), respectively, are formed. Exposure of a solution of 1 to carbon monoxide results in the very rapid formation of RuCl2(CO)2(D-P1)2 (8), thereby demonstrating the ease with which the oxygen donors are displaced from the metal and hence the hemilabile nature of the two bidentate D-P1 ligands in 1. Preliminary studies indicate that 1-7 act as catalysts for the asymmetric hydrogenation reactions of acetophenone and 3-quinuclidinone to give the corresponding alcohols in generally high conversions but low enantiomeric excesses.

show abstract

“…They are more flexible compared with the BIPHEP counterparts, which is important since non-covalent coordination of a small-compared with the ligand-hydrogenation product has to be sufficient for the chiral induction in the racemic and interconverting ligand. Although phosphinite ligands have been reported for rhodium catalyzed asymmetric hydrogenation, [29][30][31][32][33][34][35][36][37][38][39] they remain less recognized compared with other privileged chiral ligand families. In contrast to the here employed biphenol-type ligand, phosphinite ligands derived from enantiopure binaphthol are atropos.…”

Section: Resultsmentioning

confidence: 99%

Supramolecular chirality transfer in a stereodynamic catalysts

Storch

Trapp

2018

Chirality

View full text Add to dashboard Cite

We present rhodium catalysts that contain stereodynamic axially chiral biphenol-derived phosphinite ligands modified with non-stereoselective amides for non-covalent interactions. A chirality transfer was achieved with (R)- or (S)-acetylphenylalanine methyl amide, and the interaction mechanism was investigated by NMR measurements. These interactions at the non-stereoselective interaction sites and the formation of supramolecular complexes result in an enrichment of either the (R )- or (S ) enantiomer of the tropos catalysts, which in turn provide the (R)- or (S)-acetylphenylalanine methyl ester in the hydrogenation of (Z)-methyl-α-acetamidocinnamate.

show abstract

Electronic and steric effects of ligands as control elements for rhodium-catalyzed asymmetric hydrogenation

Cited by 17 publications

References 16 publications

Substituent electronic effects in chiral ligands for asymmetric catalysis

Substituent electronic effects in chiral ligands for asymmetric catalysis

Ruthenium and osmium complexes of hemilabile chiral monophosphinite ligands derived from 1D-pinitol or 1D-chiro-inositol as catalysts for asymmetric hydrogenation reactions

Supramolecular chirality transfer in a stereodynamic catalysts

Contact Info

Product

Resources

About