Chiral bis-imidazoline pincer rhodium compound, preparation and asymmetric catalysis application thereof

A bis-imidazoline clamp and rhodium compound technology, which is applied in the synthesis and application of metal organic compounds, can solve the problem of low reactivity, and achieve the effects of simple preparation, insensitivity to air and moisture, and wide application range

Active Publication Date: 2012-10-24
PHARMARON BEIJING
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  • Abstract
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  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the relatively low reactivity of ketones, there are relatively few examples of asymmetric alkynylation reactions

Method used

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  • Chiral bis-imidazoline pincer rhodium compound, preparation and asymmetric catalysis application thereof
  • Chiral bis-imidazoline pincer rhodium compound, preparation and asymmetric catalysis application thereof
  • Chiral bis-imidazoline pincer rhodium compound, preparation and asymmetric catalysis application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Embodiment one: Preparation of chiral bis-imidazoline pincer rhodium compound 1: Will( S)-1,3-bis(4-phenyl-4,5-dihydro-1-p-tolyl-1H-imidazol-2-yl)-benzene (273 mg, 0.50 mmol), RhCl 3 ·3H 2 O (131 mg, 0.50 mmol) and sodium bicarbonate (42 mg, 0.50 mmol) were added to a 50 mL three-necked flask, then methanol (10 mL) and water (2 mL) were added, and the o C was stirred for 12 h. The reaction was stopped, cooled to room temperature, concentrated, and separated by thin layer chromatography to obtain the compound 1 , yield 57%. Experimental data of this compound: M.p.: 199-202 o C. [α] D 20 = +912 ( c 0.176, CHCl 3 ).IR (KBr): ν 3422, 3177, 3029, 2921, 2857, 1577, 1490, 1404, 1254, 1159, 1106, 1038, 1022, 823, 762, 699, 522 cm -1 . 1 H NMR (400 MHz, CDCl 3 ): δ 7.58 (d, J = 7.1 Hz, 4H, ArH), 7.36 (t, J = 7.3 Hz, 4H, ArH), 7.32-7.22 (m, 10H, ArH), 6.73-6.65 (m, 3H, ArH), 5.35 (app t, J = 11.5 Hz, 2H, NCH), 4.49 (app t, J = 10.2 Hz, 2H, NC H H), 3.83...

Embodiment 2

[0031] Embodiment two: Preparation of chiral bis-imidazoline pincer rhodium compound 2: Will( S )-1,3-bis(4-benzyl-4,5-dihydro-1-p-tolyl-1H-imidazol-2-yl)-benzene (345 mg, 0.60 mmol), RhCl 3 ·3H 2 O (131 mg, 0.50 mmol) and sodium bicarbonate (46 mg, 0.55 mmol) were added to a 50 mL three-necked flask, then ethanol (10 mL) was added, and the o C stirred and reacted for 20 h. The reaction was stopped, cooled to room temperature, concentrated, and separated by thin layer chromatography to obtain the compound 2 , yield 52%. Experimental data of this compound: M.p.: 228-230 o C. [α] D 20 = +369 ( c 0.170, CHCl 3 ).IR (KBr): ν 3415, 2923, 1757, 1580, 1512, 1405, 1300, 1158, 1095, 817, 702, 466 cm -1 . 1 H NMR (400 MHz, CDCl 3 ): δ 7.31-7.26 (m, 7H, ArH), 7.23-7.17 (m, 7H, ArH), 7.11 (d, J = 8.3 Hz, 4H, ArH), 6.69-6.63 (m, 3H, ArH), 4.71-4.63 (m, 2H, NCH), 4.07 (app t, J = 10.0 Hz, 2H, NC H H), 3.81 (dd, J = 7.2, 9.7 Hz, 2H, NCH H ), 3.72 (dd, J = 3.8, 14....

Embodiment 3

[0032] Embodiment three: Synthesis of chiral bis-imidazoline pincer rhodium compound 3: Will( S , S )-1,3-bis(4,5-diphenyl-4,5-dihydro-1-cyclohexyl-1H-imidazol-2-yl)-benzene (409 mg, 0.60 mmol), RhCl 3 ·3H 2 O (131 mg, 0.50 mmol) and sodium bicarbonate (46 mg, 0.55 mmol) were added to a 50 mL three-necked flask, then methanol (10 mL) and water (2 mL) were added, and the o C stirred the reaction for 24 h. The reaction was stopped, cooled to room temperature, concentrated, and separated by thin layer chromatography to obtain the compound 3 , yield 26%. Experimental data of this compound: M.p.: 221-223 o C. [α] D 20 = +432 ( c 0.116, CHCl 3 ).IR (KBr): ν 3421, 3193, 2929, 2854, 1704, 1569, 1531, 1486, 1403, 1270, 1094, 756, 700, 475 cm -1 . 1 H NMR (400 MHz, CDCl 3 ): δ 7.82 (d, J = 8.0 Hz, 2H, ArH), 7.36-7.24 (m, 21H, ArH), 4.84 (d, J = 8.4 Hz, 2H, NCH), 4.75 (d, J = 8.4 Hz, 2H, NCH), 4.48-4.41 (m, 2H, NCy-H), 2.00-1.74 (m, 4H, CyH), 1.68-1.53 ​​(m, 4H, ...

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Abstract

The invention provides a chiral bis-imidazoline pincer rhodium compound and an asymmetric addition reaction method of ethyl trifluoropyruvate with terminal alkyne under the catalysis of the compound. Optically active trifluoromethyl propargyl tertiary alcohol is synthesized in a high enantioselectivity mode. The rhodium compound is simple in preparation, easy to modify in structure and good in stability. During an asymmetric alkynylation reaction for catalyzing the trifluoroacetone acid, the catalyst dosage is few, the reaction temperature is mild and controllable, the application range of a substrate is wide, and the product- optically active trifluoromethyl propargyl tertiary alcohol has a high yield and an enantio-selectivity higher than 95% in most instances.

Description

technical field [0001] The invention belongs to the technical field of synthesis and application of metal-organic compounds, and relates to the preparation of a class of chiral bis-imidazoline pincer rhodium compounds and the asymmetric addition of trifluoropyruvate to terminal alkynes under the catalysis of such compounds Reaction, high enantioselective synthesis of optically active trifluoromethyl propargyl tertiary alcohol. Background technique [0002] Optically active propargyl tertiary alcohols are important intermediates of various drugs and natural products, and are also very useful synthetic building blocks in organic synthesis. Under the action of chiral catalysts (usually including metals and chiral ligands), prochiral The asymmetric alkynylation of sex ketones is one of the most direct and efficient methods for the synthesis of these compounds. However, due to the relatively low reactivity of ketones, examples of asymmetric alkynylation reactions are relatively ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00B01J31/22C07B41/02C07C67/343C07C69/732C07C69/734C07D333/24
Inventor 宋毛平王涛龚军芳牛俊龙郝新奇
Owner PHARMARON BEIJING
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