Sulfonamide type chiral monophosphine ligand as well as preparation method and application thereof

A sulfenamide and chiral technology, applied in the field of chiral monophosphine ligands and their preparation, can solve problems such as long synthetic routes, restrictions on the development of chiral phosphine ligands, and difficulty in transformation

Inactive Publication Date: 2018-11-23
EAST CHINA NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, problems such as expensive raw materials, long synthetic routes, low yields, and difficult transformation largely restrict the development of chiral phosphine ligands.

Method used

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  • Sulfonamide type chiral monophosphine ligand as well as preparation method and application thereof
  • Sulfonamide type chiral monophosphine ligand as well as preparation method and application thereof
  • Sulfonamide type chiral monophosphine ligand as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 11a

[0045] Example 1 1a(S, R s )Synthesis

[0046] In a 250mL dry single-necked flask, add the borane complex of dicyclohexylphosphine (8mmol) and dry mixed solvent of toluene and tetrahydrofuran (50ml) under nitrogen atmosphere, and stir at -78°C for 10 minutes After that, n-butyllithium (1.0eq., 8mL, 1.6M) was added dropwise. Stirring was continued for 1.5 hours, and o-dibromobenzene (8mmol) was added, followed by n-butyllithium (8mmol, 1.6M). 30 minutes to join (9.6 mmol), then warmed to room temperature and stirred overnight. Thereafter, methyl trifluoromethanesulfonate (12 mmol) was added to the reaction system. Subsequently, select dry solvent, add Et 2 NH (8mL), stirred overnight at 50°C, spin-dried, and purified by column chromatography to obtain The yield was 50%. Proton NMR (300MHz, CDCl 3 )δ7.76-7.72 (m, 1H), 7.49-7.38 (m, 2H), 7.30-7.27 (m, 1H), 7.25-7.15 (m, 5H), 6.87 (d, J=10.1Hz, 1H) , 2.57(s, 3H), 1.91-1.41(m, 11H), 1.28-0.85(s, 20H). Phosphine NMR (122M...

Embodiment 21b

[0047] Example 2 1b(S, R s )Synthesis

[0048] Concrete operation with reference to embodiment 1, raw material used is The yield was 55%. Proton NMR (300MHz, CDCl 3 )δ7.73-7.69 (m, 1H), 7.48-7.37 (m, 2H), 7.28-7.23 (m, 1H), 7.07-7.01 (m, 4H), 6.82 (d, J=10.1Hz, 1H) , 2.56(s, 3H), 2.27(s, 3H), 1.91-0.87(m, 31H). Phosphine NMR (122MHz, CDCl 3 )δ-16.88. Carbon NMR (126MHz, CDCl 3 )δ147.37(d, J=22.2Hz), 137.02, 136.71, 134.93(d, J=21.1Hz), 132.95(d, J=3.2Hz), 130.41, 128.65, 128.57, 128.10(d, J=4.9 Hz), 126.43, 69.79(d, J=31.6Hz), 58.49, 34.67(dd, J=22.3, 13.1Hz), 30.63(d, J=18.0Hz), 29.98-29.34(m), 27.17-26.55( m), 26.26 (d, J=24.5Hz), 24.09, 21.00. High resolution mass spectrometry theoretical data C 30 h 45 NOPS: m / z (%): 512.3116 (M+H + ), experimental data: 512.3120.

Embodiment 31c

[0049] Example 3 1c(S, R s ) synthesis (reference scheme 1)

[0050] Concrete operation with reference to embodiment 1, raw material used is The yield was 43%. Proton NMR (300MHz, CDCl 3 ( s, 3H), 1.89-1.45 (m, 11H), 1.23-0.85 (m, 20H). Phosphine NMR (122MHz, CDCl 3 )δ-17.02. Fluorine NMR (282MHz, CDCl 3 )δ-115.16 (tt, J=8.1, 5.0Hz). Carbon NMR (126MHz, CDCl 3 )δ161.86 (d, J=246.5Hz), 146.90 (d, J=22.1Hz), 135.84 (d, J=3.3Hz), 134.84 (d, J=21.4Hz), 133.22 (d, J=3.3 Hz), 132.37(d, J=8.1Hz), 128.92, 127.76(d, J=4.8Hz), 126.73, 114.70(d, J=21.3Hz), 69.58(d, J=32.2Hz), 58.62, 34.69 high Resolution Mass Spectrometry Data C 30 h 45 NOPS: m / z (%): 516.2865 (M+H + ), experimental data: 516.2860.

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Abstract

The invention discloses a sulfonamide type chiral monophosphine ligand. The chiral monophosphine ligand is a compound shown as a formula I in the description. The invention also discloses a syntheticmethod of the ligand. The method comprises the following steps of using compounds shown as a formula (2) R<1>R<2>PH.BH3, a formula (3) in the description, a formula (4) in the description and a formula (5) R<5>X as raw materials; performing substitution reaction and addition reaction for preparing the ligand by a one-pot method. The enantiomer (as shown in the description) of the formula (1) of the ligand can be realized by using the enantiomer (as shown in the description) of the formula (4) of the ligand. By using the chiral sulfoimide of two structures, the two kinds of optical pure chiralmonophosphine ligands (S, Rs) and (R, Ss) can be obtained. The invention also discloses application of the ligand to catalysis of asymmetrical reduction Heck reaction in O-halogenated aryl allyl ethermolecules; high reaction activity and three-dimensional selectivity are realized; wide application values are realized.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry and relates to novel sulfenamide chiral monophosphine ligands and their preparation methods and applications, in particular to a class of novel chiral monophosphine ligands and their preparation methods and applications. Background technique [0002] Chirality exists widely in nature and is one of the basic properties of nature. In organisms, the vast majority of biomolecules such as proteins, nucleotides, and sugars are chiral molecules. Chiral substances are like people's left and right hands. The two enantiomers are mirror images of each other but cannot be completely superimposed. Seemingly similar two enantiomers often have different optical properties, physicochemical properties and different or even opposite biological activities, such as chiral ethambutol. Its (S, S) configuration isomer can treat tuberculosis, while (R, R) configuration isomer can cause blindness. It can be s...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/50B01J31/24C07D307/79C07D409/06C07D307/80
CPCB01J31/2404C07B2200/07C07D307/79C07D307/80C07D409/06C07F9/5022C07F9/505Y02P20/55
Inventor 张俊良许冰张展鸣
Owner EAST CHINA NORMAL UNIV
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