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Chiral monophosphine ligand CF-Phos of pyridine skeleton, and preparation method and application thereof

A cf-phos and pyridine technology, which is applied to the new chiral monophosphine ligand CF-Phos modified by pyridine skeleton and its preparation field, can solve the problems of expensive raw materials, complex synthesis routes, hazardous reagents and the like

Active Publication Date: 2019-04-23
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The purpose of this invention is to provide a class of novel chiral monophosphine ligand CF-Phos and its preparation method and application, overcome in the synthetic research technology of existing phosphine-containing chiral ligand (catalyst), expensive raw material, synthetic Due to the disadvantages of complex routes and high hazards of reaction reagents, the chiral monophosphine ligand CF-Phos in all stereoconfigurations can be prepared efficiently, with high selectivity and at low cost by using different metal reagents.

Method used

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  • Chiral monophosphine ligand CF-Phos of pyridine skeleton, and preparation method and application thereof
  • Chiral monophosphine ligand CF-Phos of pyridine skeleton, and preparation method and application thereof
  • Chiral monophosphine ligand CF-Phos of pyridine skeleton, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0108] Example 1 The synthesis (reference scheme one)

[0109] Step 1: In a 250mL single-necked flask, add (20mmol, 3.72g), ethylene glycol (3.0eq., 3.72g), TsOH (0.1eq., 0.38g) and 50mL Toluene, install a water separator, heat and reflux at 150°C for 5 hours, and slowly cool to room temperature Liquid separation, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, washed with water and saturated sodium chloride respectively, dried over anhydrous sodium sulfate, filtered, spin-dried, and purified by column chromatography to obtain The yield was 95%.

[0110] Wherein, TsOH is p-toluenesulfonic acid, and Toluene is toluene.

[0111] The second step: the prepared in the first step (10mmol, 2.3g) was added to a 100mL dry reaction eggplant-shaped flask, under argon protection, 30mL THF was added, and KPPh was added at -50°C 2 (1.2eq., 24mL, 0.5 M inTHF), after stirring for 1 hour, the temperature was raised naturally, stirred o...

Embodiment 2

[0118] Example 2 The synthesis (reference scheme one)

[0119] The specific operation is the same as in Example 1, and the raw materials used are replaced by The yield was 76%. 1 H NMR (300MHz, CDCl 3 )δ7.52–7.43(m,1H),7.42–7.30(m,10H),7.10(d,J=76.0Hz,1H),7.02(d,J=9.0Hz,1H),4.92(s,1H ), 4.56(d, J=6.0Hz, 1H), 1.40(d, J=9.0Hz, 3H), 1.30(s, 9H); 31 P NMR (122MHz, CDCl 3 )δ-3.09; 13 C NMR (101MHz, CDCl 3 ), 23.32, 21.64. HRMS (ESI) calculated for [C 23 h 28 N 2 OPS][M+H] + :411.1655; found: 411.1656.

Embodiment 3

[0120] Example 3 The synthesis (reference scheme one)

[0121] The specific operation was the same as in Example 1, except that the metal reagent used was changed to tert-butylmagnesium bromide (4eq., 4mL, 1M inTHF), and the yield was 63%. 1 H NMR (400MHz, CDCl 3 )δ7.41(td, J=8.0,2.4Hz,1H),7.38–7.20(m,10H),7.04(dd,J=8.0,2.0Hz,1H),6.98(d,J=8.0Hz,1H ),5.07(d,J=8.0Hz,1H),3.93(d,J=8.0Hz,1H),1.03(s,9H),0.72(s,9H); 31 P NMR (122MHz, CDCl 3 )δ-2.70; 13 C NMR (101MHz, CDCl 3 )δ161.62,159.76(d,J=8.1Hz),136.57(d,J=9.1Hz),135.96(d,J=9.1Hz),135.29(d,J=5.12Hz),134.90,134.70,134.10,133.91 , 129.09, 128.76–128.29(m), 127.22, 126.95, 122.52, 68.32, 56.00, 36.47, 26.58, 22.99. HRMS (ESI) calculated for [C 26 h 34 N 2 OPS][M+H] + :453.2124; found: 453.2116.

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Abstract

The invention discloses chiral monophosphine ligand CF-Phos of a pyridine skeleton, and a preparation method and application thereof. The monophosphine ligand is a compound 1, or an enantiomer, a racemate and a diastereomer of the compound 1. The preparation method of the ligand includes taking compounds as shown in the specification as raw materials, and subjecting the raw materials to condensation reaction, substitution reaction, hydrolysis reaction and addition reaction to prepare the monophosphine ligand; or taking compounds as shown in the specification as raw materials, subjecting the raw materials to condensation reaction to obtain reactants, subjecting the reactants and a compound as shown in the specification to addition reaction to prepare the monophosphine ligand. Through the addition reaction between the compounds with two configurations and different types of metal reagents, the chiral monophosphine ligand, namely an optically pure compound with four general configurationsof 1(S, Rs), 1 (R, Rs), 1 (S, Ss) and 1 (R, Ss) can be obtained. The invention further discloses the application of the ligand in copper-catalyzed asymmetric lactonization reaction of unsaturated carboxylic acid, and the ligand has wide application value.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry and relates to a novel chiral monophosphine ligand and its preparation method and application, in particular to a class of novel chiral monophosphine ligand CF-Phos modified with a pyridine skeleton and its preparation method and application. Background technique [0002] Chirality is a basic property that widely exists in nature, and two substances that are mutually chiral can exhibit completely different properties. Common living substances such as proteins (composed of L-type amino acids), DNA and RNA (composed of D configuration of ribose), etc., all have specific chirality. It can be seen that the study of chiral compounds is an urgent and important task. So far, there have been many ways to obtain optically pure compounds, such as chiral resolution, induced transformation of chiral compounds, and asymmetric catalysis. Asymmetric catalysis is characterized by mild reaction conditio...

Claims

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Application Information

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IPC IPC(8): C07F9/58B01J31/24C07D413/06
CPCB01J31/2404B01J2231/00C07B2200/07C07D413/06
Inventor 张俊良陈晓峰周璐佳
Owner EAST CHINA NORMAL UNIV
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