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3, 3'-position biaryl group binaphthyl shaft chiral phosphoramidite ligand and preparation method thereof

A phosphoramidite and axial chiral technology, applied in the field of new chiral phosphoramidite ligands, can solve the problem of low enantioselectivity

Inactive Publication Date: 2009-10-28
TIANJIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example: the reported chiral catalyst is applied to the addition reaction of alkyl zinc to α-alkene-β-carbonyl carboxylate and α-alkene, and the enantioselectivity is lower than 70%.

Method used

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  • 3, 3'-position biaryl group binaphthyl shaft chiral phosphoramidite ligand and preparation method thereof
  • 3, 3'-position biaryl group binaphthyl shaft chiral phosphoramidite ligand and preparation method thereof
  • 3, 3'-position biaryl group binaphthyl shaft chiral phosphoramidite ligand and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0021] Example 1: Ligand (R)-3,3'-bis(4-biphenyl)-2,2'-binaphthol-N, the preparation of N-dimethylphosphoramidite:

[0022] Under the protection of argon, (R) 3,3'-4-phenyl-phenyl-1,1'-binaphthyl-2,2'-diol 591mg (1.0mmol), hexamethylphosphorous Add 163mg (1.0mmol) of triamine into a 20mL Schlenk reaction flask, and add 5mL of dry toluene, heat at 110°C for 12 hours, and the reaction is complete as detected by thin-layer chromatography. The reaction mixture was evaporated to remove the solvent, and separated by flash silica gel column (petroleum ether / ethyl acetate=20 / 1 as the eluent) to obtain the target product, 560 mg, with a yield of 85.0%. 1 H NMR (500MHz, CDCl 3 ), δppm: 2.48 (s, 6H, 2×CH 3 ), 7.25(s, 8H, Ar-H), 7.30(m, 2H, Ar-H), 7.35(m, 2H, Ar-H), 7.45(d, J=8.5Hz, 4H, Ar-H) , 7.48(d, J=8.5Hz, 2H, Ar-H), 7.63(d, J=8.5Hz, 2H, Ar-H), 7.45(d, J=8.5Hz, 4H, Ar-H), 7.80 (m, 2H, Ar-H), 8.40 (d, J = 8.5 Hz, 2H, Ar-H).

[0023]

[0024] The ligand is coordinated with copp...

example 2

[0025] Example 2: Ligand (S)-3,3'-bis(4-biphenyl)-2,2'-binaphthol-N, the preparation of N-dimethylphosphoramidite:

[0026] Method similar to Example 1, with (S) 3,3'-4-phenyl-phenyl-1,1'-binaphthyl-2,2'-diphenol and hexamethylphosphorous triamide as raw materials , with toluene as the solvent, the reaction temperature was 110°C, and the corresponding ligand was synthesized with a yield of 83%. 1 H NMR (500MHz, CDCl 3 ), δppm: 2.47 (s, 6H, 2×CH 3 ), 7.25(s, 8H, Ar-H), 7.32(m, 2H, Ar-H), 7.38(m, 2H, Ar-H), 7.45(d, J=8.5Hz, 4H, Ar-H) , 7.48(d, J=8.5Hz, 2H, Ar-H), 7.65(d, J=8.5Hz, 2H, Ar-H), 7.45(d, J=8.5Hz, 4H, Ar-H), 7.81 (m, 2H, Ar-H), 8.41 (d, J = 8.5 Hz, 2H, Ar-H).

[0027]

[0028] The ligand is coordinated with copper trifluoromethanesulfonate to catalyze the conjugated addition reaction of diethylzinc and α-ylidene malonate to obtain the addition product with a yield of 80% and enantioselectivity The ee value reaches 85%.

example 3

[0029] Example 3: Ligand (S)-3,3'-bis(4-biphenyl)-2,2'-binaphthol-N, the preparation of N-diethylphosphoramidite:

[0030] Method similar to example 1, with (S) 3,3'-4-phenyl-phenyl-1,1'-binaphthyl-2,2'-diphenol and hexaethylphosphorous triamide as raw materials , using benzene as a solvent, the reaction temperature is 100°C, and the corresponding ligand is synthesized with a yield of 76%. 1 H NMR (500MHz, CDCl 3 ), δppm: 1.02(t, 6H, 2×CH 3 ), 2.60 (dd, J=8.5Hz, J=15.5Hz, 4H, 2×CH 2 ), 7.25(s, 8H, Ar-H), 7.32(m, 2H, Ar-H), 7.38(m, 2H, Ar-H), 7.45(d, J=8.5Hz, 4H, Ar-H) , 7.48(d, J=8.5Hz, 2H, Ar-H), 7.65(d, J=8.5Hz, 2H, Ar-H), 7.45(d, J=8.5Hz, 4H, Ar-H), 7.81 (m, 2H, Ar-H), 8.41 (d, J = 8.5 Hz, 2H, Ar-H).

[0031]

[0032] The ligand is coordinated with copper trifluoromethanesulfonate to catalyze the conjugated addition reaction of diethyl zinc and α-ylidene-β-carbonyl carboxylate to obtain the addition product with a yield of 92%. The enantioselectivity ee value reach...

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Abstract

The invention relates to a 3, 3'-position binaphthyl shaft chiral phosphoramidite ligand containing biaryl group and a preparation method thereof. The preparation method comprises the following steps of: leading 3, 3'-dual-biaryl group-2, 2'-dinaphthol to react with hexagon-alkyl group phosphoramidite in organic solvent at the temperature of 0-120 DEG C according to the mol rate of 1:1, or leading 3, 3'- dual-biaryl group-2, 2'-dinaphthol to react with phosphorus trichloride and dialkyl amine in steps, and after complete reaction, the object chiral phosphoramidite ligand can be obtained through washing, extraction and separation. After going through complexation with metallic copper salt, the chiral phosphoramidite ligand can be used for catalyzing the conjugate addition reaction of zinc alkyl with alpha, beta-unsaturated carbonyl compounds, and an additional product is prepared with high yield up to 78-98% and high enantioselectivity ee value up to 80-98%.

Description

technical field [0001] The invention relates to a class of novel chiral phosphoramidite ligands, and specifically discloses a class of chiral phosphoramidite ligands containing a 3,3'-position biaryl binaphthyl axis and a preparation method thereof. Background technique [0002] Chiral phosphoramidites are a class of important organocatalytic ligands, which exhibit certain chiral induction ability in metal-catalyzed asymmetric reactions (Ben.L.Feringa, Acc.Chem.Res.2000, 33, 346 -353). In recent years, some chiral phosphoramidite ligands have been designed and synthesized. For example, people such as Netherlands Feringa have designed and synthesized chiral phosphoramidite ligands using a chiral binaphthyl skeleton (Ben.L.Feringa, et al., J.Org.Chem., 2008,73,940-947), Alexakis et al. utilize tartaric acid derivatives to synthesize another class of chiral phosphoramidite ligands (Alexandre Alexakis, et al., Tetrahedron: Asymmetry., 2001, 12, 1151-1157), these chiral ligands...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/6571B01J31/24C07B53/00C07B37/02
Inventor 马军安王琏聂晶崔汉峰
Owner TIANJIN UNIV
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