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1,2-disubstituted bis ruthenium face chirality ligand and method for synthesizing same

A technology of ruthenocene faces and chiral ligands, which is applied in 1 field and can solve problems such as low ligand reactivity and poor asymmetry induction effect

Inactive Publication Date: 2008-03-12
SHANGHAI JIAO TONG UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The disadvantage is that the reactivity of the ligand is low, and the asymmetric induction effect is still poor.

Method used

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  • 1,2-disubstituted bis ruthenium face chirality ligand and method for synthesizing same
  • 1,2-disubstituted bis ruthenium face chirality ligand and method for synthesizing same

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] 1, the preparation of 1-dicarboxyruthenocene (1)

[0032] Add ruthenocene (0.23g, 1mmol), m-chlorobenzoyl chloride (0.18g, 1mol) and dichloromethane (5mL) into a 250mL two-necked flask. Cool down to 0-2°C, add anhydrous aluminum trichloride (0.14 g, 1 mmol) in batches, wait for the temperature to rise naturally and stir overnight. Cool down to 0-2°C, add water (2mL) carefully, stir for 2h, then dilute the system with dichloromethane (20mL), wash with 10% sodium hydroxide solution, water and saturated brine successively, and anhydrous Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure. The residue was subjected to column chromatography (ethyl acetate / petroleum ether=1 / 20) to obtain an acylated product (51.5 mg, y=13.9%).

[0033] 1 H NMR (400MHz, CDCl 3 ): δ4.64(s, 5H), 4.83(tJ=2Hz, 2H), 5.01(tJ=2Hz, 2H), 7.28-7.55(m, 4H), 7.99-8.05(m, 1H).

[0034] 2-Chlorobenzoylruthenocene (8.2g, 22mmol) and potassium tert-butoxide (9.9g, 88mmol) were adde...

Embodiment 2

[0044] 1, the preparation of 1-dicarboxyruthenocene (1)

[0045] Into a 250 mL two-necked flask were added ruthenocene (0.23 g, 1 mmol), m-chlorobenzoyl chloride (2.7 g, 15 mol) and dichloromethane (5 mL). Cool down to 0-2°C, add anhydrous aluminum trichloride (0.42g, 3mmol) in batches, wait for the temperature to rise naturally and stir overnight. Cool down to 0-2°C, add water (2mL) carefully, stir for 2h, then dilute the system with dichloromethane (20mL), wash with 10% sodium hydroxide solution, water and saturated brine successively, and anhydrous Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure. The residue was subjected to column chromatography (ethyl acetate / petroleum ether=1 / 20) to obtain an acylated product (168 mg, y=65.4%).

[0046] 1 H NMR (400MHz, CDCl 3 ): δ4.64(s, 5H), 4.83(t J=2 Hz, 2H), 5.01(t J=2 Hz, 2H), 7.28-7.55(m, 4H), 7.99-8.05(m, 1H) .

[0047] 2-Chlorobenzoylruthenocene (8.2g, 22mmol) and potassium tert-butoxide (9.9g, 8...

Embodiment 3

[0057] 1, the preparation of 1-dicarboxyruthenocene (1)

[0058] Add ruthenocene (11.6 g, 50 mmol), m-chlorobenzoyl chloride (63 mL, 0.5 mol) and dichloromethane (100 mL) into a 250 mL two-necked flask. Cool down to 0-2°C, add anhydrous aluminum trichloride (8.7 g, 65 mmol) in batches, wait for the temperature to rise naturally and stir overnight. Cool down to 0-2°C, add water (20mL) carefully, stir for 2h, then dilute the system with toluene (200mL), wash with 10% sodium hydroxide solution, water and saturated brine successively, anhydrous Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure. The residue was subjected to column chromatography (ethyl acetate / petroleum ether=1 / 20) to obtain an acylated product (13.5 g, y=73%).

[0059] 1 H NMR (400MHz, CDCl 3 ): δ4.64(s, 5H), 4.83(tJ=2Hz, 2H), 5.01(tJ=2Hz, 2H), 7.28-7.55(m, 4H), 7.99-8.05(m, 1H).

[0060]2-Chlorobenzoylruthenocene (8.2g, 22mmol) and potassium tert-butoxide (9.9g, 88mmol) were added to...

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Abstract

The present invention relates to 1, 2- substitute cyclopentadienyl ruthenium surface chiral ligand in the chemical field and the correspondence synthetic method. The present invention comprises six reaction steps: the cyclopentadienyl ruthenium, after the Fuke acyl reaction, is hydrolyzed into 1-carboxyl cyclopentadienyl ruthenium; then 1-carboxyl cyclopentadienyl ruthenium reacts with oxalyl chloride to generate 1-carboxyl carbonyl cyclopentadienyl ruthenium; 1-oxazoline carboxyl carbonyl cyclopentadienyl ruthenium reacts with beta-amino alcohol to generate lactam compound, and then reacts with methane-sulfonyl chloride to generate 1-oxazoline cyclopentadienyl ruthenium; 1-oxazoline cyclopentadienyl ruthenium reacts with sec-butyllithium first, and then reacts with diphenyl chloride phosphate to generate (S, Sp)-1,2-substitute cyclopentadienyl ruthenium P, N- ligand; 1-oxazoline cyclopentadienyl ruthenium reacts with sec-butyllithium first, and then reacts with trimethylchlorosilane to generate (S,Sp)-1- oxazoline-2-trimethyl cyclopentadienyl ruthenium. Then the trimethyl is shucked off to generate (S,Rp)-1,2-substitute cyclopentadienyl ruthenium P,N- ligand. The structure is as follows: in the formula: R: a represents isopropyl, b represents tert-butyl.

Description

technical field [0001] The invention relates to a chiral ligand in the technical field of chemical engineering and a synthesis method thereof, in particular to a 1,2-disubstituted ruthenocene chiral ligand used in asymmetric catalytic reactions and a synthesis method thereof. technical background [0002] The rapid rise of the chiral drug industry is mainly due to the great development of asymmetric synthesis methodology research, and in turn, the chiral drug industry has promoted the research of asymmetric synthesis methodology. Asymmetric catalytic organic synthesis is one of the most effective and beneficial methods to obtain chiral compounds. In asymmetric catalytic organic synthesis, the key to high reactivity and high enantioselectivity lies in the structure of chiral ligands. Among them, the synthesis and application of chiral phosphine nitrogen ligands have always been valued by chemists. [0003] Found through literature search to prior art, Sammakia et al publish...

Claims

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Application Information

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IPC IPC(8): C07F17/02
CPCC07B2200/07C07F17/02C07B53/00B01J31/189C07C29/145
Inventor 张万斌谢芳刘德龙
Owner SHANGHAI JIAO TONG UNIV
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