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Phosphorus-oxazoline ligand with spiro backbone and its uses in asymmetrical catalytic hydrogenation

A technology of oxazoline and ligand is applied in the synthesis field of novel chiral spirocyclic phosphine-oxazoline ligand and its ionic iridium complex, and achieves the effect of high stereoselectivity and high reactivity

Active Publication Date: 2006-12-27
NANKAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Such ligands often show high activity in asymmetric imine hydrogenation reactions, but only give moderate enantioselectivity (Schnider, P.; Koch, G.; Pretot, R.; Wang, G. .; Bohnen, M.; Kruger, C.; Pfaltz, A.Chem.Eur.J.1997, 3, 887.), so the development of more effective phosphine-oxazoline ligands and catalysts for imine compounds Asymmetric hydrogenation has important application value

Method used

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  • Phosphorus-oxazoline ligand with spiro backbone and its uses in asymmetrical catalytic hydrogenation
  • Phosphorus-oxazoline ligand with spiro backbone and its uses in asymmetrical catalytic hydrogenation
  • Phosphorus-oxazoline ligand with spiro backbone and its uses in asymmetrical catalytic hydrogenation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Example 1: Preparation of (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spirodihydroindane

[0035]

[0036] Add (S)-1,1'-spirodihydroindane-7,7'-diphenol (5.0g, 19.8mmol), pyridine (7.0mL, 86.7mmol) and 100mL dichloromethane into a 250mL reaction flask, ice The salt bath was cooled to below 0°C, and trifluoromethanesulfonic anhydride (8.2 mL, 43.7 mmol) was added dropwise from a constant pressure dropping funnel under temperature control. After the addition, the mixture was naturally warmed to room temperature and stirred overnight. Rotary evaporation precipitation, the residue was dissolved in 80mL ethyl acetate, transferred to a separatory funnel, and 5% HCl solution, saturated saline, saturated NaHCO 3 solution, washed with saturated brine successively, anhydrous Na 2 SO 4 dry. After filtering and removing the solvent, an appropriate amount of dichloromethane was dissolved, passed through a short column of silica gel, and rinsed with dichloromethane. The so...

Embodiment 2

[0037] Example 2: Preparation of (S)-7-diphenylphosphono-7'-trifluoromethanesulfonyloxy-1,1'-spirodihydroindene

[0038]

[0039] Add (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spirodihydroindane (4.0 g, 7.75 mmol), diphenylphosphine oxide (3.13 g, 15.5 mmol), palladium acetate (87 mg, 0.39 mmol), 1,4-bis(diphenylphosphino)ylbutane (dppb, 166 mg, 0.39 mmol), and 25 mL of degassed DMSO. Electromagnetic stirring was used to make it fully mixed. After adding N,N-diisopropylethylamine (4.1 g, 32 mmol), the mixture was heated at 100° C. in an oil bath and reacted for 6 hours. Cool to room temperature, dilute with ethyl acetate, separate, 5% HCl solution, saturated saline, saturated NaHCO 3 solution, washed with saturated brine successively, anhydrous Na 2 SO 4 dry. After filtering and removing the solvent, use silica gel column chromatography (eluent: petroleum ether / EtOAc=3:1) to obtain (S)-7-diphenylphosphono-7'-trifluoromethanesulfonyloxy - 4.0 g of 1,1'-spiroindane,...

Embodiment 3

[0040] Example 3: Preparation of (S)-7-bis(p-methoxyphenyl)phosphono-7'-trifluoromethanesulfonyloxy-1,1'-spiroindene

[0041] Prepared with (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spirodihydroindane and bis-p-methoxyphenylphosphonous acid, the method is the same as in Example 2 same. A white solid was obtained, yield: 90%. Mp 150-152°C; [α] 8 D -216(c 0.5, CH 2 Cl 2 ); 1 H NMR (300MHz, CDCl 3 )δ2.20-2.32 (m, 3H, CH 2 ), 3.04-3.18 (m, 3H, CH 2 ), 3.20-3.40 (m, 2H, CH 2 ), 3.78(s, 3H, OCH 3 ), 3.85(s, 3H, OCH 3 ), 6.24(d, 2H, J=8.1Hz, Ar-H), 6.80-6.85(m, 4H, Ar-H), 6.86-7.00(m, 2H, Ar-H), 7.16-7.21(m, 4H, Ar-H), 7.21-7.30 (m, 2H, Ar-H), 7.32 (d, 1H, J=7.2Hz, Ar-H); 31 PNMR (121MHz, CDCl 3 )δ31.45(s); 13 C NMR (75MHz, CDCl 3 )δ29.7, 30.1, 30.8, 38.7, 38.9, 54.2, 60.8, 112.4, 112.6, 116.3, 118.8, 121.1, 122.6, 124.9, 125.1, 125.9, 126.4, 126.9, 127.2, 127.4, 127.8, 132.9 , 132.5, 139.7, 143.8, 144.8, 145.0, 148.6, 151.7, 160.7, 160.9; MS (EI) m / z 628 (M + ...

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Abstract

The invention relates to a new chiral toroid phosphine oxazoline ligand and its ionic iridium complex compound, and the application of said iridium complex compound in asymmetric catalytic hydrogenization for imines. The toroid phosphine oxazoline ligand is a widely used compound, for example, used as chiral ligand for asymmetric catalytic hydrogenization; especially said iridium complex compound is characterized by high stereoselectivity for asymmetric catalytic hydrogenization, the ee value reaches 97% and high reactive activity.

Description

technical field [0001] The present invention relates to a kind of synthetic method of novel chiral spiro phosphine-oxazoline ligand and its ionic iridium complex, and the ionic iridium complex of the phosphine-oxazoline ligand in different imines Applications in symmetric catalytic hydrogenation. Background technique [0002] Asymmetric catalytic synthesis is a hotspot in the field of organic synthetic chemistry research (Ohkuma, T.; Kitamura, M.; Noyori, R. Catalytic Asymmetric Synthesis, Wiley, New York, 2000). The key to asymmetric catalytic synthesis is how to design and synthesize chiral catalysts with high enantioselectivity and catalytic activity. The design and synthesis of chiral catalysts is, in a sense, the design and synthesis of chiral ligands, because chiral ligands are the source of asymmetric induction and control of chiral catalysts. In 1966, Wilkinson found that the highly active homogeneous catalyst triphenylphosphine rhodium complex provided a premise f...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/653C07F9/6558C07F15/00B01J23/44
Inventor 周其林朱守非王立新
Owner NANKAI UNIV
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