A class of ferrocenoquinoline compounds with face chirality and its synthesis method

A chiral ferrocene and compound technology, applied in chemical instruments and methods, organic chemistry, metallocene and other directions, to achieve the effect of less reaction steps and high yield

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

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Problems solved by technology

Therefore, it is very important to develop a new chiral NAD(P)H mimic, but there are the following difficulties: 1) the introduction of the chiral environment of the chiral NAD(P)H mimic; 2) how to realize the chiral NAD(P)H Circular regeneration of P)H simulants; 3) Whether chiral NAD(P)H simulants can achieve hydrogen conversion process and achieve excellent enantioselectivity

Method used

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  • A class of ferrocenoquinoline compounds with face chirality and its synthesis method
  • A class of ferrocenoquinoline compounds with face chirality and its synthesis method
  • A class of ferrocenoquinoline compounds with face chirality and its synthesis method

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] The synthesis of embodiment 1 compound 2

[0032]

[0033] Under nitrogen protection, add compound 1 (1.049g, 3.1mmol) and 10mL EtOH to a 100mL reaction flask, raise the temperature to 40°C, and slowly add NaBH 4 (176mg, 4.5mmol), stirred overnight. Add 10mL H 2 O quenches the reaction. Dichloromethane extraction, anhydrous Na 2 SO 4 After drying, column chromatography gave 0.960 g of a light yellow solid with a yield of 91%.

Embodiment 2

[0034] The synthesis of embodiment 2 compound 4a

[0035]

[0036] Under nitrogen protection, compound 2 (260mg, 0.76mmol), compound 3a (230mmg, 1.52mmol), Pd(OAc) were added to the 50mL reaction flask 2 (34mg, 0.152mmol), Ba(OH) 2 ·8H 2 O (480 mg, 1.52 mmol), 10 mL ethanol and 1 mL water. Raise the temperature to 100°C and react overnight. Cool to room temperature, add 20mL H 2 O, dichloromethane extraction, anhydrous Na 2 SO 4 Drying and column chromatography gave 0.170 g of a light yellow solid with a yield of 73%. 1 H NMR (400MHz, CDCl 3 )δ7.67(dd, J=7.6,1.5Hz,1H),7.18-7.12(m,1H),6.92-6.86(m,1H),6.72(dd,J=7.9,0.8Hz,1H),4.46 (t,J=6.5,5.1Hz,1H),4.30-4.27(m,3H),4.23(s,5H),3.76(s,2H); 13 C NMR (100MHz, CDCl 3 )δ144.6, 133.0, 128.3, 123.2, 119.5, 116.1, 87.7, 85.9, 71.0, 69.6, 69.5, 67.6, 59.9. HRMS: Calculated for C 17 h 17 56 FeNONa[M+Na] + 330.0557,found 330.0555.

Embodiment 3

[0037] The synthesis of embodiment 3 compound 4b

[0038]

[0039] Under nitrogen protection, compound 2 (260mg, 0.76mmol), compound 3b (254mmg, 1.52mmol), Pd(OAc) were added to the 50mL reaction flask 2 (34mg, 0.152mmol), Ba(OH) 2 ·8H 2 O (480 mg, 1.52 mmol), 10 mL ethanol and 1 mL water. Raise the temperature to 100°C and react overnight. Cool to room temperature, add 20mL H 2 O, dichloromethane extraction, anhydrous Na 2 SO 4 After drying, column chromatography gave 0.186 g of a light yellow solid with a yield of 73%. 1 H NMR (400MHz, CDCl 3 )δ7.57 (d, J = 8.4Hz, 1H), 6.46 (dd, J = 8.4, 2.4Hz, 1H), 6.28 (d, J = 2.4Hz, 1H), 4.46 (s, 1H), 4.31- 4.25(m,3H),4.25-4.19(m,6H),3.80(s,3H),3.64(brs,3H); 13 C NMR (100MHz, CDCl 3)δ160.0, 145.8, 133.8, 115.4, 104.9, 101.7, 87.5, 86.4, 70.8, 69.5, 67.5, 60.0, 55.3. HRMS Calculated for C 18 h 19 56 FeNO 2 Na[M+Na] + 360.0663,found 360.0656.

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Abstract

The invention provides a ferroceno quinoline compound with planar chirality as shown in description, R1-R8 are H or C1-C10 alkyl, the C1-C10 alkyl comprises one or multiple substituents of the methoxyand halogen. The invention further provides a synthesis method of the compound, the o-iodine ferrocenecarboxaldehyde is used as an initial raw material, the o-iodine ferrocenylmethanol is obtained through a reduction method, the cross-coupling with the o-amino phenylboronic acid is realized by utilizing the palladium-promoted coupled reaction, and then the ring closing can be realized under an oxidizing condition, thereby obtaining the ferroceno quinoline compound with the planar chirality. The compound is less in reaction step and high in yield; the synthesized ferroceno quinoline compound with the planar chirality is free from splitting and is a chiral pure reagent; the synthesized ferroceno quinoline compound with the planar chirality can be used as the recyclable transhydrogenase reagent under a hydrogen condition, thereby effectively realizing the asymmetric hydrogenation on the C=N, C=O, C=C and heteroaromatic compound.

Description

technical field [0001] The invention relates to the design and synthesis method of a class of ferrocenoquinoline compounds with face chirality. Background technique [0002] In organisms, more than 400 chemical reactions require the participation of coenzymes, among which NAD(P)H, as an important coenzyme in organisms, plays a vital role in the process of transferring protons and electrons. Biomimetic hydrogenation is an important research part in the field of asymmetric hydrogenation, and different types of NAD(P)H simulants have emerged. Traditional NAD(P)H mimics mainly refer to Hantzsch ester or phenanthridine (document: a) Xu, H.J.; Liu, Y.C.; Fu, Y.; Wu, Y.D.Org.Lett.2006, 8, 3449; b) Chen, Q-A.; Gao, K.; Duan, Y.; Ye, Z.-S.; Shi, L.; Yang Y.; c) Chen, Q.-A.; Chen, M.-W.; Yu, C.-B.; Shi, L.; Wang, D.-S.; Yang, Y.; Zhou, Y.-G.J. Am. Chem. Soc. 2011, 133, 16432; d) Fleischer, S.; Zhou, S.; Junge, K.; Beller, M. Angew. Chem. Int. Ed. 2013, 52, 5120; , L.-Q.; Li, Y.; J...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F17/02
Inventor 王杰孙蕾周永贵
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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