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Dicyclopentadienyl iron pocket ligand possessing central chirality and planar chirality, synthesis method and uses

A ferrocene, chiral technology, applied in the field of synthesis of ferrocene pocket ligands

Inactive Publication Date: 2006-02-15
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

No palladium-catalyzed asymmetric allylation of open-chain simple carbonyls has been reported

Method used

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  • Dicyclopentadienyl iron pocket ligand possessing central chirality and planar chirality, synthesis method and uses
  • Dicyclopentadienyl iron pocket ligand possessing central chirality and planar chirality, synthesis method and uses
  • Dicyclopentadienyl iron pocket ligand possessing central chirality and planar chirality, synthesis method and uses

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Embodiment 1: the synthesis of ferrocene bis-imide phosphine ligand

[0024] At room temperature, add (1.0mmol) ferrocene aldehyde phosphine and (0.5mmol) chiral diamine and 5ml toluene to the reaction flask, then add molecular sieves and catalytic amount of 0.05mmol p-toluenesulfonic acid, reflux and stir for five hours, diatoms Filtrate with soil, remove the solvent under reduced pressure, and recrystallize from petroleum ether to obtain the corresponding bis-imidophosphine ligand.

[0025] (R,R,Sp,Sp)-P1(R 1 and R 2 =-(CH 2 ) 4 -, Ar=Ph)

[0026] Yield: 62%; mp: 184°C; [α] D 20 =+276.6° (c=0.34, CHCl 3 ); 1 H NMR (300MHz, CDCl 3 ): δ1.23-1.42(m, 6H), 1.61-1.64(m, 2H), 3.01-3.04(m, 2H), 3.78(s, 2H), 4.11(s, 10H), 4.37-4.39(m , 2H), 4.92(s, 2H), 7.14-7.59(m, 20H), 8.23(d, J=1.8Hz, 2H); 31 P NMR (161.92MHz, CDCl 3 ): δ-20.11; MS (EI) m / z (rel) 875 (M + +1, 15.25), 810 (100.00), 397 (18.39), 121 (10.51). IR (KBr): 2924, 2854, 1649, 1640, 1433, 102...

Embodiment 2

[0035] Embodiment 2: synthesis of ferrocene diamine phosphine ligand

[0036] At room temperature, dissolve 10 mmol of bis-imidophosphine ligand in 20 ml of ethanol, add 12 mmol of sodium borohydride to reflux for 6 hours, add water to treat unreacted sodium borohydride, extract with ether, wash the organic phase with saturated ammonium chloride, and the product Separation and purification by column chromatography.

[0037] (R,R,Sp,Sp)-P6(R 1 and R 2 =-(CH 2 ) 4 -, Ar=Ph)

[0038] Yield: 65%; [α] D 20 =-336.1° (c=0.47, CHCl 3 ); 1 H NMR (300MHz, CDCl 3 ): δ1.36-1.61(m, 8H), 1.88(m, 2H), 3.55(d, J=2.1Hz, 4H), 3.63(s, 10H), 3.74(s, 2H), 4.24(s, 2H), 4.37(s, 2H), 7.16-7.56(m, 20H); 31 P NMR (161.92MHz, CDCl 3 ): δ-22.95; MS (EI) m / z (rel) 877 (M + +1, 20.01), 812 (100), 399 (18.56), 121 (9.63). IR (KBr): 3056, 2926, 1587, 1106, 742, 697cm -1 ;Elemental Analysis C 52 h 52 Fe 2 N 2 P 2 : Calculated C, 71.08; H, 5.97; N, 3.19. Found C, 70.80; H, 6...

Embodiment 3

[0046] Example 3: Asymmetric allylation of α-methoxyacetophenone

[0047] Under argon protection, [Pd(C 3 h 5 )Cl] 2 (1.6mg, 0.00437mmol) and ligand (0.0962mmol) were dissolved in 1mL tetrahydrofuran, and refluxed for 0.5 hours. Another reaction tube contained α-methoxyacetophenone (0.174mmol) in 0.5mL tetrahydrofuran, Add LHMDS (0.21mL1M in THF, 0.21mmol) under cooling in a dry ice-acetone bath, keep this temperature for 0.5 hours, add the catalyst prepared on site, allyl acetate (0.262mmol) and additive AgBr (0.0174mmol), stir for 10min, Then the temperature was raised to -20°C for reaction. The reaction was tracked by TLC, the reaction was quenched by adding saturated brine, the layers were separated, the aqueous phase was extracted with ether (3×10 mL), the organic phases were combined, and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure and purified by column chromatography. Yield: 97%; ee(%): 93%; 1 H NMR (300MHz, CDCl 3 ): δ...

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Abstract

The invention relates to a ferrocene ligand having central chirality and planar chirality, method for synthesizing and use thereof. The ligand has the central chirality of diamines, and is obtained through condensation of ferrocene phosphine aldehyde and chiral diamine, and further reduction, the ligand can be purified through recrystallization and column chromatography. The ligand can be used as catalyst in asymmetric alkylation reaction.

Description

technical field [0001] The invention relates to a class of chiral ligands, synthesis methods and uses, that is, the synthesis and use of a ferrocene pocket ligand with central chirality and planar chirality. Background technique [0002] Allyl substitution reaction is one of the more effective methods for constructing C-C bonds. Its asymmetric allylation of cyclic carbonyls and open-chain activated carbonyls yielded many good results. For the asymmetric allylation of simple carbonyls, however, not many good results have been achieved. No palladium-catalyzed asymmetric allylation of open-chain simple carbonyls has been reported. Pocket ligands have a good asymmetric induction effect in the asymmetric allylation reaction of simple carbonyl compounds. How to design and synthesize a new class of ligands with simple structure, easy synthesis and good catalytic activity is simple A hot direction in the study of asymmetric allylation of carbonyl compounds. Contents of the inve...

Claims

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Application Information

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IPC IPC(8): C07F17/02C07F9/28B01J31/22C07B53/00
Inventor 严小霞梁春根侯雪龙
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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