New chiral aminophosphine carboxyphosphinite ligands (AMPCP). Synthesis and application in asymmetric hydrogenation and hydroformylation

Naïli, Saïd; Mortreux, André; Agbossou, Francine

doi:10.1016/s0957-4166(98)00363-2

Cited by 13 publications

(10 citation statements)

References 32 publications

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“…for C 25 H 41 N 4 P: C, 70.04; H, 9.66; N, 13.07. Found: C, 69.94; H, 9.60; N, 12.91%); d H (300.1 MHz, CDCl 3 ) 1.10 (d, 3 J HH = 6.6 Hz, 12H, ((CH 3 ) 2 CH) 2 N), 1.27 (d, 3 J HH = 6.6 Hz, 12H, ((CH 3 ) 2 CH) 2 N), 2.34 (s, 6H, m-CH 3 C 6 H 3 ), 3.54 (sept, 3 J HH = 6.6 Hz, 4H, ((CH 3 ) 2 CH) 2 N) 2 ), 6.34 (s, 1H, H 4 ), 6.83 (s, 1H, p-C 6 H 3 ), 6.84 (s, 2H, o-C 6 H 3 ), 7.12 (d, 3 J HH = 2.9 Hz, 1H, H 3 ), 7.23 (s, 1H, H 5 ), 8.96 (d, 4 (2,4,6 -Trimethylphenyl)(bis(diisopropylamino)phosphanyl)(1Hpyrrol-2-ylmethylene)amine 4c. Using an analogous procedure to that for the preparation of 4a, compound 2c (1.56 g, 7.4 × 10 −3 mol) in DME (20 cm 3 ) was reacted with Bu n Li (4.6 cm 3 , 7.4 × 10 −3 mol; 1.6 mol dm −3 , solution in hexanes) and (Pr i 2 N) 2 PCl (1.97 g, 7.4 × 10 −3 mol) in DME (20 cm 3 ).…”

Section: Attempted Preparation Of Phenyl[1-(1h-pyrrol-2-yl)ethylidene...mentioning

confidence: 99%

“…for C 29 H 49 N 4 P: C, 71.84; H, 10.21; N, 11.56. Found: C, 71.97; H, 10.10; N, 11.49%); d H (400.1 MHz, CDCl 3 ): d 1.18 (d, 3 J HH = 6.8 Hz, 12H, ((CH 3 ) 2 CH) 2 N), 1.31 (d, 3 J HH = 6.8 Hz, 12H, ((CH 3 ) 2 CH) 2 C 6 H 3 ), 1.37 (d, 3 J HH = 6.8 Hz, 12H, ((CH 3 ) 2 CH) 2 N), 3.24 (sept, 3 J HH = 6.7 Hz, 2H, o-((CH 3 ) 2 CH) 2 C 6 H 3 ), 3.72 (sept, 3 J HH = 6.8 Hz, 4H, ((CH 3 ) 2 CH) 2 N), 6.50 (s, 1H, H 4 ), 7.23 (m, 1H, H 3 ), 7.28 (s, 2H, m-C 6 H 3 ), 7.29 (s, 1H, p-C 6 H 3 ), 7.38 (d, 3 J HH = 3.5 Hz, 1H, H 5 ), 8.79 (d, 4 (1-Diphenylphosphanyl-1H -pyrrol-2-ylmethylene)phenylamine rhodium carbonyl chloride 5a. In a glove box, a Young's tap NMR tube was charged with 3a (0.044 g, 1.2 × 10 −4 mol), [Rh(CO) 2 Cl] 2 (0.025 g, 6.4 × 10 −5 mol) and sealed before transferring to a Schlenk line.…”

Section: Attempted Preparation Of Phenyl[1-(1h-pyrrol-2-yl)ethylidene...mentioning

confidence: 99%

“…To a stirred solution of [PdCl 2 (COD)] (0.49 g, 1.7 × 10 −3 mol) in CH 2 Cl 2 (10 cm 3 ), a solution of 4d (0.89 g, 1.8 × 10 −3 mol) in CH 2 Cl 2 (10 cm 3 ) was added via cannula and the mixture was allowed to stir for 18 h. The volatile components were then removed in vacuo and the yellow-orange oil extracted with hexane (20 cm 3 ) to afford 14d (0.95 g, 85%) as a dark yellow crystalline solid following removal of volatiles under vacuum (Anal. Calc 3 J HH = 6.9 Hz, 6H, o-((CH 3 ) 2 CH) 2 C 6 H 3 ), 1.31 (d, 3 J HH = 6.7 Hz, 12H, ((CH 3 ) 2 CH) 2 N), 1.42 (d, 3 J HH = 6.9 Hz, 6H, o-((CH 3 ) 2 CH) 2 C 6 H 3 ), 1.47 (d, 3 J HH = 6.7 Hz, 12H, ((CH 3 ) 2 CH) 2 N), 3.22 (sept, 3 J HH = 6.9 Hz, 2H, o-((CH 3 ) 2 CH) 2 C 6 H 3 ), 4.47 (dsept, 3 J HH = 6.9 Hz, 3 J PH = 2.0 Hz, 4H, ((CH 3 ) 2 CH) 2 N), 6.59 (t, 3 J HH = 3.0 Hz, 1H, H 4 ), 7.01 (m, 1H, H 3 ), 7.12 (s, 1H, p-C 6 H 3 ), 7.15 (s, 2H, m-C 6 H 3 ), 7.83 (d, 4…”

Section: Alternative Preparation Of (35-dimethylphenyl)(1-diphenylpho...mentioning

confidence: 99%

“…Ease and flexibility of synthesis are important considerations for ligand systems designed for applications in catalysis, facilitating study of the important correlation between catalyst structure, properties and performance. Bidentate P-N ligands have been particularly successful in this regard, 1,2 and have been exploited in a wide variety of metal-catalysed processes, including transfer hydrogenation, 3 asymmetric hydroformylation, 4 olefin oligomerisation/polymerisation, 5-8 co-polymerisation, 9,10 and coupling reactions. 11, 12 The heteroditopic nature of such ligands has been used to engender both control and selectivity in reactions occurring at metal centres; the significant electronic asymmetry that is possible having a considerable impact.…”

Section: Introductionmentioning

confidence: 99%

“…(m, 3H, m/p-C 6 H 5 ), 7.29 (t,3 J HH = 7.8 Hz, 2H, o-C 6 H 5 ), 7.49 (s, 1H, H 5 ), 7.94 (d,4 J PH = 2.7 Hz, 1H, CH=N); d C { 1 H} NMR (100.6 MHz, CDCl 3 ) 24.1 (d,3 J CP = 2.7 Hz, ((CH 3 ) 2 CH) 2 N), 50.2 (d, 2 J PC = 12.1 Hz, ((CH 3 ) 2 CH) 2 N), 112.5 (s, C 4 ), 124.0 (s, o-C 6 H 5 ), 126.5 (s, p-C 6 H 5 ), 128.3 (s, m-C 6 H 5 ), 129.2 (s, C 3 ), 130.3 (s, C 5 ), 130.4 (s, C 2 ), 153.0 (s, i-C 6 H 5 ), 155.8 (d, 3 J PC = 6.4 Hz, CH=N), 188.9 (dd, 1 J RhC = 79.6 Hz; 2 J PC = 21.5 Hz, RhCO); d P { 1 H} (121.5 MHz, CDCl 3 ) +117.9 (d, 1 J RhP = 233 Hz); IR (KBr, CDCl 3 ) 1590 (m CN ), = 2005 (m CO ) cm −1 . Dimethylphenyl)(bis(diisopropyl)aminophosphanyl)(1H-pyrrol-2-ylmethylene)amine rhodium carbonyl chloride 6b.…”

mentioning

confidence: 99%

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Chelating N-pyrrolylphosphino-N′-arylaldimine ligands: synthesis, ligand behaviour and applications in catalysis

et al. 2006

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Two families of variously-substituted N-pyrrolylphosphino-N'-arylaldimine ligands, 2-(aryl-N=CH)C4H3N-PR2 {R=Ph; R=Pri2N}, have been prepared from the corresponding pyrrolylaldimines . The donor characteristics/basicity of P-N-chelating and have been assessed using a combination of 31P{1H} NMR and IR spectroscopies through study of the magnitudes of 1JSeP for the phosphorus(V) selenides and , and measurement of nu(CO) for the complexes [RhCl(CO)(-kappa2-P,N)], respectively. The synthesis of the palladium(II) complexes [PdCl2(-kappa2-P,N)] was readily achieved from reaction of or with [PdCl2(MeCN)2] in CH2Cl2. X-Ray crystallographic studies of and confirm the chelating nature of the P-N ligands, which adopt a distorted 'envelope' conformation, and highlight the potentially significant steric demands of these metal scaffolds. Reaction of equimolar quantities of with [NiBr2(DME)] in MeCN afforded [NiBr2(-kappa2-P,N)], while the same reaction undertaken in CH2Cl2 with gave rise to the homoleptic bis(pyrrolatoimine) derivative [Ni{2-(mes-N=CH)C4H3N}2] in 45% yield, following P-N bond cleavage. Complex was characterised in the solid-state by X-ray crystallography. No identifiable metal-containing complexes could be obtained on reaction of with a variety of sources of Ni(II). The palladium dichloride complexes and proved inactive in combination with MAO or EtAlCl2 for ethylene polymerisation, and with methanesulfonic acid for CO/ethylene co-polymerisation. Contrastingly, the nickel complexes in combination with 4.5 eq. EtAlCl2 catalysed the formation of butenes and hexenes with moderate activity from ethylene at 1 bar.

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Section: Attempted Preparation Of Phenyl[1-(1h-pyrrol-2-yl)ethylidene...mentioning

confidence: 99%

Section: Attempted Preparation Of Phenyl[1-(1h-pyrrol-2-yl)ethylidene...mentioning

confidence: 99%

Section: Alternative Preparation Of (35-dimethylphenyl)(1-diphenylpho...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Chelating N-pyrrolylphosphino-N′-arylaldimine ligands: synthesis, ligand behaviour and applications in catalysis

et al. 2006

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Enantioselective Hydroformylation

2021

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Hydroformylation is powerful catalytic reaction capable of converting alkenes directly into aldehydes by addition of a formyl group and hydrogen across the double bond. Installation of the formyl group at an internal carbon establishes a chiral center, and a variety of chiral ligands may be employed to direct the enantioselectivity of the reaction. The alkene substrates are easily accessed, and the resultant aldehydes are common precursors for diverse synthetic manipulations. This chapter covers enantioselective hydroformylation from its inception, presents the most common metal precursors and ligands, and includes all examples that produce aldehydes with yields above 20% and enantioselectivity above 60:40 er. The initial discussion focuses on the mechanism and stereochemistry, and on the regio‐ and enantioselectivity‐determining steps in particular, as these are crucial for overall yield. The “Scope and Limitations” section is divided by substrate type and offers examples of exceptional catalytic systems that have been reported for each. The application of enantioselective hydroformylation to synthetic procedures is discussed by highlighting some reported examples, comparing it to other protocols that also afford chiral aldehydes, and exploring the standard experimental conditions. The intention of this review is to demonstrate the power and scope of enantioselective hydroformylation to researchers, and to provide a suitable starting point for those interested in its application to their own synthetic strategies.

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ChemInform Abstract: New Chiral Aminophosphine Carboxyphosphinite Ligands (AMPCP). Synthesis and Application in Asymmetric Hydrogenation and Hydroformylation.

1999

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New chiral aminophosphine carboxyphosphinite ligands (AMPCP). Synthesis and application in asymmetric hydrogenation and hydroformylation

Cited by 13 publications

References 32 publications

Chelating N-pyrrolylphosphino-N′-arylaldimine ligands: synthesis, ligand behaviour and applications in catalysis

Chelating N-pyrrolylphosphino-N′-arylaldimine ligands: synthesis, ligand behaviour and applications in catalysis

Enantioselective Hydroformylation

ChemInform Abstract: New Chiral Aminophosphine Carboxyphosphinite Ligands (AMPCP). Synthesis and Application in Asymmetric Hydrogenation and Hydroformylation.

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