Axial chirality diamine compound induced by central chirality and synthetic method

A bisamine compound and chiral induction technology, applied in the direction of organic chemistry, can solve problems such as limitations in industrialization and application, and achieve the effect of easy raw materials, simplified synthesis process, and simple synthesis process

Inactive Publication Date: 2009-10-07
王春江
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Because chemical resolution is a cumbersome and empirical work, the staff will spend a lot of time on the resolution process, and even finally have to resort to the method of preparative HPLC to obtain optically pure chiral diamines, which is the ultimate Industrial promotion and application have caused restrictions

Method used

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  • Axial chirality diamine compound induced by central chirality and synthetic method
  • Axial chirality diamine compound induced by central chirality and synthetic method
  • Axial chirality diamine compound induced by central chirality and synthetic method

Examples

Experimental program
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Effect test

Embodiment 1

[0035] Synthesis of (R, R)-2,4-bis[(2-iodo-3-nitro)phenoxy]pentane (1a)

[0036] Dissolve 2-iodo-3-nitrophenol (2.8g, 0.01mol) in 25mL N, N-dimethylformamide, then add potassium carbonate (4.14g, 0.03mol), (2S, 4S)-2, 4-Pentanediol bis-p-toluenesulfonate (6.00mmol), heated at 80°C until the reaction was complete (TLC tracking), and distilled off most of N,N-dimethylformamide under reduced pressure, after adding water, CH 2 Cl 2 The organic phases were extracted and combined, washed with water and saturated brine respectively, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 5.26 g of light yellow powder product compound (1a) with a yield of 88%. [α] 25 D =-169.8 (c 0.40, CHCl 3 ); 1 H NMR (CDCl 3 , TMS, 300MHz) δ1.44(d, J=5.7Hz, 6H), 2.13~2.17(m, 2H), 4.83~4.87(m, 2H), 6.82(d, J=8.1Hz, 2H), 7.10 (d, J=8.1Hz, 2H), 7.18~7.7.24(t, 2H); 13 C NMR (CDCl 3 , TMS, 75MHz) δ20.33, 44.78, 73.98, 81.35, 115.97, 116.89, 130.33, 155.58, 158.16; H...

Embodiment 2

[0038] Synthesis of (S, S)-2,4-bis[(2-iodo-3-nitro)phenoxy]pentane (1b)

[0039]2-iodo-3-nitrophenol (2.8g, 0.01mol) was dissolved in 25mL N,N-dimethylformamide, and potassium carbonate (4.14g, 0.03mol) was added, (2R, 4R)-2 , 4-pentanediol bis-p-toluenesulfonate (6.00mmol), heated at 50°C until the reaction was complete (TLC tracking), and distilled off most of N,N-dimethylformamide under reduced pressure, after adding water, CH 2 Cl 2 The organic phases were extracted and combined, washed with water and saturated brine respectively, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 5.26 g of light yellow powder product compound (1b) with a yield of 88%. [α] 25 D =+169.8 (c 0.40, CHCl 3 ); 1 H NMR (CDCl 3 , TMS, 300MHz) δ1.44(d, J=5.7Hz, 6H), 2.13~2.17(m, 2H), 4.83~4.87(m, 2H), 6.82(d, J=8.1Hz, 2H), 7.10 (d, J=8.1Hz, 2H), 7.18~7.7.24(t, 2H); 13 C NMR (CDCl 3 , TMS, 75MHz) δ20.33, 44.78, 73.98, 81.35, 115.97, 116.89, 130.33, 155.58, ...

Embodiment 3

[0041] Synthesis of (R, R)-2,4-bis([(2-iodo-3-nitro)phenoxy]pentane (1a)

[0042] Dissolve 2-iodo-3-nitrophenol (2.8g, 0.01mol) in 25mL N,N-dimethylformamide, then add potassium carbonate (0.05mol), (2S,4S)-2,4-pentane Diol bis-p-methanesulfonate (0.01mmol), heated at 100°C until the reaction was complete (TLC tracking), and distilled off most of N,N-dimethylformamide under reduced pressure, after adding water, CH 2 Cl 2 The organic phases were extracted and combined, washed with water and saturated brine respectively, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 5.26 g of light yellow powder product compound (1a) with a yield of 88%.

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Abstract

Axial chirality diamine compound induced by central chirality, in formula, X and Y are hydrogen, bromine, chlorine, iodine, methyl or aryl. The invention comprises the following steps: reacting 2-iodine-3-nitrophenol with 2,4-pentanediol with central chirality or derivate to gain 2,4-bi[(2-iodine-3-nitryl)phenoxy]pentane; coupling and restoring to gain (S)-[6,6'-((R,R)-2,4-pentanediol oxygen)]-2,2'-biamino-1,1'-biphenyl or (R)-[6,6'-((S,S)-2,4-pentanediol oxygen)]-2,2'-biamino-1,1'-biphenyldiamine; reacting the axial chirality biphenyldiamine induced by central chirality with the halogenating reagent to gain enantiomer pure 3,3'-dihalo or 3,3', 5,5'-tetrahalo axial chirality biphenyldiamine; and then Suzuki coupling enantiomer pure 3,3'-dihalo or 3,3', 5,5'-tetrahalo axial chirality biphenyldiamine to produce enantiomer pure 3,3'-dimethyl or aryl or 3,3', 5,5'-tetramethyl or aryl axial chirality biphenyldiamine. The invention has advantages of easily-gained raw material and simple operation. A series of enantiomer pure diamine produced by the invention can be applied to a series of asymemetric reaction.

Description

technical field [0001] The invention relates to an axial chiral diamine compound based on central chirality induction and a synthesis method thereof. Background technique [0002] Since William S. Knowles and Ryoji Noyori first applied chiral phosphine ligands and ruthenium complexes as catalysts for homogeneous asymmetric hydrogenation in the 1960s, the synthesis of chiral phosphine ligands has been continuously innovated, including The representative ones are DIOP and BINAP series, and there are C 2 The chiral skeletons of symmetrical binaphthyl and biphenyl play a very important role in the synthesis of chiral bidentate phosphine ligands. [0003] by having C 2 Symmetrical chiral diamine compounds can be easily prepared with C 2 Symmetrical chiral bidentate ligands of phosphoramidites. However, usually with C 2 The symmetrical chiral diamine skeleton with biphenyl or binaphthyl needs to be obtained by resolving the racemic diamine compound with a chiral reagent. Bec...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D321/00
Inventor 王春江陶海燕
Owner 王春江
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