A class of NAD(P)H stimulants with planar chiral cyclophane quinoline skeleton, synthesis method and applications thereof

A synthesis method and simulant technology, applied in organic chemistry methods, organic compound/hydride/coordination complex catalysts, chemical instruments and methods, etc., can solve problems such as poor stability, difficulty, cumbersome synthesis, etc., and achieve reaction steps The effect of less and easy operation

Active Publication Date: 2020-05-08
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to its ferrocene skeleton, the compound has poor stability, relatively cumbersome and difficult synthesis, and ideal reactivity

Method used

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  • A class of NAD(P)H stimulants with planar chiral cyclophane quinoline skeleton, synthesis method and applications thereof
  • A class of NAD(P)H stimulants with planar chiral cyclophane quinoline skeleton, synthesis method and applications thereof
  • A class of NAD(P)H stimulants with planar chiral cyclophane quinoline skeleton, synthesis method and applications thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] Embodiment 1: the synthesis of compound 2

[0047]

[0048] Under nitrogen protection, compound 1 (1.900g, 7.16mmol), NIS (1.933g, 8.59mmol), Pd(OAc) were added to a 250mL reaction flask 2 (0.322g, 1.43mmol), AgCO 2 CF 3 (0.316g, 1.43mmol), 120mL 1,2-dichloroethane. The temperature was raised to 110°C and the reaction was stirred. Diatomaceous earth assisted filtration, and column chromatography gave 2.269 g of a yellow solid, with a yield of 81%. 1 HNMR (400MHz, CDCl 3 )δ8.05(d,J=1.1Hz,1H),7.01(d,J=7.8Hz,1H),6.59(dd,J=9.1,4.5Hz,2H),6.52(dd,J=12.6,4.8 Hz,2H),6.46(d,J=7.7Hz,1H),4.03(d,J=0.8Hz,3H),3.84–3.73(m,1H),3.46(t,J=10.6Hz,1H), 3.21–2.94(m,5H),2.87(m,1H); 13 C NMR (100MHz, CDCl 3 )δ153.5,143.8,140.7,139.6,138.8,135.0,134.3,133.5,133.2,132.9,130.0,128.6,110.1,62.2,39.98,35.0,34.7,33.1. HRMS: Calculated for C 18 h 19 INO[M+H] + 392.0506,found 392.0507.

Embodiment 2

[0049] Embodiment 2: the synthesis of compound 2

[0050]

[0051] Under nitrogen protection, compound 1 (200mg, 0.76mmol), NBS (163mg, 0.91mmol), Pd(OAc) were added to the 50mL reaction flask 2 (34mg, 0.15mmol), AgCO 2 CF 3 (34mg, 0.15mmol), 15mL 1,2-dichloroethane. The temperature was raised to 110°C and the reaction was stirred. Diatomaceous earth assisted filtration, and column chromatography gave 145 mg of white solid, yield 55%.

Embodiment 3

[0052] Embodiment 3: the synthesis of compound 3

[0053]

[0054] Compound 2 (1.200 g, 3.07 mmol), p-benzenemethanesulfonic acid monohydrate (1.168 g, 6.14 mmol), aqueous formaldehyde (4.6 mL, 61.40 mmol), 10 mL tetrahydrofuran and 1 mL water were added to a 25 mL sealed tube. The temperature was raised to 130° C., and the reaction was carried out for 72 hours. Cool to room temperature, add 10mL H 2 O, dichloromethane extraction, anhydrous Na 2 SO 4 Drying and column chromatography gave 1.046 g of a yellow solid with a yield of 94%. 1 H NMR (400MHz, CDCl 3 )δ9.79(s,1H),6.98(dd,J=7.9,1.8Hz,1H),6.68–6.56(m,3H),6.49(dd,J=7.9,1.8Hz,1H),6.38(dd ,J=7.9,1.8Hz,1H),3.88(m,1H),3.63–3.49(m,1H),3.25–3.15(m,3H),3.09–2.96(m,2H),2.81(m,1H ). 13 C NMR (100MHz, CDCl 3 )δ197.8,144.6,144.2,139.8,138.8,137.0,135.4,135.3,133.2,132.8,131.1,128.8,111.1,39.2,35.0,34.3,33.1. HRMS: Calculated for C 17 h 16 IO[M+H] + 363.0240,found 363.0244.

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Abstract

The invention relates to design and synthesis of a class of NAD(P)H stimulants with a planar chiral cyclophane quinoline skeleton. According to the synthesis, optically pure cyclophane formaldoxime ether is used as an initial raw material; o-iodo cyclophane formaldoxime ether can be obtained through a carbon-hydrogen bond activation method; o-iodo cyclophane formaldehyde can be obtained by utilizing an acid-promoted hydrolysis reaction; o-iodo cyclophane methanol can be obtained through a reduction method; o-iodo cyclophane methanol and o-aminophenylboronic acid or boron ester are subjected tocross coupling under a palladium catalyzed coupling reaction; and finally oxidative cyclization is achieved under an oxidation condition so as to obtain a class of NAD(P)H stimulants with the planarchiral cyclophane quinoline skeleton. According to the invention, the optically pure NAD(P)H stimulant with a planar chiral cyclophane quinoline skeleton can be effectively synthesized, and can be used as a recyclable chiral NAD(P)H stimulant under a hydrogen condition to realize asymmetric hydrogenation of C=N, aromatic heterocyclic compounds.

Description

technical field [0001] The invention relates to a class of NAD(P)H simulants with a chiral cycloarkanoquinoline skeleton and a synthesis method and application thereof, belonging to the field of organic synthesis and biomimetic asymmetric catalytic reduction. Background technique [0002] Biomimetic science is an ancient and young subject, which mainly studies the structure and working principle of living things. Based on these principles, new technologies and equipment have been developed to improve people's living standards and quality of life. In living organisms, nicotinamide adenine dinucleotide (NADH) and nicotinamide adenine dinucleotide phosphate (NADPH) are a very important class of coenzymes that play a crucial role in the transfer of protons and electrons . The process mainly depends on the interconversion between reduced NAD(P)H and oxidized NAD(P)+. NADPH is mainly produced in the pentose phosphate pathway and participates in the synthesis of nucleic acids an...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D221/22B01J31/02C07D215/06C07D241/44
CPCB01J31/0244B01J2231/646C07B2200/07C07D215/06C07D221/22C07D241/44
Inventor 周永贵朱周豪王杰陈木旺孙蕾
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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