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Cyclohexanediamine-derived phosphamide chiral ligand as well as preparation method thereof and application thereof

A technology of cyclohexanediamine and chiral ligands is applied in the field of new phosphoramide chiral ligands, which can solve the problems of harsh reaction conditions and large amount of chiral ligands.

Inactive Publication Date: 2013-01-30
FUJIAN INST OF RES ON THE STRUCTURE OF MATTER CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] Phosphoramide chiral ligands show good catalytic activity in many of the above asymmetric reactions, but there are also many problems, such as a large amount of chiral ligands, harsh reaction conditions, and the need to add transition metals (such as Ti(i-OPr ) 4 ), etc. Therefore, it is still of great significance to design, synthesize and screen new high-efficiency chiral phosphoramide ligands

Method used

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  • Cyclohexanediamine-derived phosphamide chiral ligand as well as preparation method thereof and application thereof
  • Cyclohexanediamine-derived phosphamide chiral ligand as well as preparation method thereof and application thereof
  • Cyclohexanediamine-derived phosphamide chiral ligand as well as preparation method thereof and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Example 1: Synthesis of (1R,2R)-1-N,1-N-diethyl-2-N-(diphenylphosphoryl)-1,2-cyclohexanediamine:

[0030] In a 25 mL two-necked flask, add compound 4 (314 mg, 1.0 mmol), 5 mL acetonitrile, potassium carbonate (690 mg, 5.0 mmol), and iodoethane (780 mg, 5.0 mmol), and reflux for 4 h. TLC detection and tracking until the reaction is complete. Add 15 mL of saturated sodium bicarbonate solution, extract with dichloromethane (10 mL × 3), combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, evaporate the solvent under reduced pressure, and separate by flash column chromatography (wash The removal agent was methanol / dichloromethane (volume ratio 1:40) to obtain 293 mg of white solid, yield: 79%. Melting point: 112-113 o C; measured by optical rotation = -62.5 (c 1.00, CH 2 Cl 2 ); Nuclear magnetic analysis (Burker AVANCE 400 spectrometer): 1 H NMR (400 MHz, CDCl 3 ): δ 1.00 (t, J = 7.0 Hz, 6H), 1.06-1.26 (m, 4H), 1.45-1.53 ​​(m, 1H),...

Embodiment 2

[0033] Example 2: Synthesis of (1R, 2R)-1-N-cyclopentyl-2-N-(diphenylphosphoryl)-1,2-cyclohexanediamine:

[0034] In a similar manner to Example 1, using 1,4-diiodobutane (620 mg, 2.0 mmol) instead of iodoethane (780 mg, 5.0 mmol), 313 mg of white solid was obtained, yield: 85%. Melting point: 99-101 o C; Rotation value measured = -31.8 (c 1.00, CH 2 Cl 2 ); Nuclear magnetic analysis (Burker AVANCE 400 spectrometer): 1 H NMR (400 MHz, CDCl 3 ): δ 0.91-1.41 (m, 5H), 1.44-1.60 (m, 1H), 1.63-1.88 (m, 6H), 1.92-2.06 (m, 1H), 2.44-2.84 (m, 4H), 3.11- 3.29 (m, 1H), 4.62-4.98 (br, 1H), 7.36-7.62 (m, 6H), 7.72-8.02 (m, 4H). 13 C NMR (100 MHz, CDCl 3 ): δ 21.8, 23.6, 24.1, 24.8, 33.8, 47.1, 53.0, 63.3 (d, J = 8.1 Hz), 128.1 (d, J = 12.7 Hz), 128.3 (d, J = 12.4 Hz), 131.2 (d , J = 9.7 Hz), 131.3 (d, J = 5.7 Hz), 131.4 (d, J = 11.1 Hz), 132.1(d, J = 9.4 Hz), 134.2 (d, J = 124.2 Hz), 134.4 (d , J = 130.2 Hz). 31 P NMR (162 MHz, CDCl 3 ): δ 22.7.

[0035]

[0036] The ligand is used to catal...

Embodiment 3

[0037] Example 3: Synthesis of (1R, 2R)-1-N-ethyl-2-N-(diphenylphosphoryl)-1,2-cyclohexanediamine:

[0038] In a method similar to Example 1, iodoethane (312 mg, 2.0 mmol) was used instead of iodoethane (780 mg, 5.0 mmol) to obtain 287 mg of white solid, yield: 85%. Melting point: 123-125 o C; Rotation value measured = -30.9 (c 1.00, CH 2 Cl 2 ); Nuclear magnetic analysis (Burker AVANCE 400 spectrometer): 1 H NMR (400 MHz, CDCl 3 ): δ 1.03-1.11 (m, 1H), 1.15-1.20 (m, 3H), 1.21-1.36 (m, 2H), 1.59-1.73 (m, 2H), 2.02-2.17 (m, 2H), 2.30- 2.49 (m, 2H), 2.49-2.62 (m, 2H), 2.74-2.97 (m, 2H), 3.51-3.65 (m, 1H), 7.41-7.60 (m, 6H), 7.80-8.00 (m, 4H) ); 13 C NMR (100 MHz, CDCl 3 ): δ 15.3, 24.6, 24.9, 31.1, 35.0 (d, J = 3.43 Hz), 40.9, 55.4, 62.8 (d, J = 5.29 Hz), 128.5 (q, J = 6.35 Hz), 131.7, 131.8, 132.1 , 132.2, 132.4, 132.6, 133.7, 133.8. 31 P NMR (162 MHz, CDCl 3 ): δ 26.6.

[0039]

[0040] The ligand is used to catalyze the asymmetric addition reaction of diethyl zinc to benzaldehy...

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Abstract

The invention provides a cyclohexanediamine-derived phosphamide chiral ligand as well as a preparation method thereof and an application thereof. The method comprises the following steps of: first, protecting one amino of chiral source cyclohexanediamine by using phthalic anhydride; and after the chiral source cyclohexanediamine is acylated with dialkyl phosphoryl chloride, removing a protecting group by using hydrazine hydrate; and performing N-alkylation reaction on the chiral source cyclohexanediamine and halohydrocarbon, so as to obtain the phosphamide chiral ligand. According to the invention, the phosphamide chiral ligand can be used for catalyzing asymmetric addition reaction of zinc alkyl and a carbonyl compound; the yield of an addition product is high up to 99 %; and the enanitomer selectivity ee value is high up to 96 %.

Description

Technical field [0001] The present invention relates to a new type of phosphoramide chiral ligands, and specifically discloses a type of cyclohexanediamine-derived phosphoramide chiral ligands and a preparation method thereof. Background technique [0002] In the field of asymmetric catalytic synthesis, the design and synthesis of highly efficient and highly catalytically active chiral ligands has always been the research focus of chemists. [0003] Chiral phosphoramides are an important class of organocatalytic ligands, which exhibit good chirality inducing ability in asymmetric catalytic reactions (Non-Patent Document 1: Zhang Zhanjin, Wan Boshun, Chen Huilin. Hand in asymmetric synthesis Catalytic phosphine (phosphorus) ester (amide) catalyst. Synthetic Chemistry, 2004, 12, 237-244). [0004] In 1993, the Japanese Soai et al. first combined the synthesized thiophosphoramide ligand (formula 1, a) with Ti(i-OPr) 4 Together, it is used to catalyze the asymmetric addition of ethyl zi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/36B01J31/24
CPCY02P20/55
Inventor 宋玲黄华银宗华边广岭
Owner FUJIAN INST OF RES ON THE STRUCTURE OF MATTER CHINESE ACAD OF SCI
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