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Polycyclic ketone preparation method

A technology of polycyclic ketones and structural formulas, applied in the field of preparation of polycyclic ketones, can solve the problems of insufficient atom economy and long steps, and achieve the effect of large theoretical innovation value, short steps and good compatibility

Active Publication Date: 2016-08-10
ZHEJIANG NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The usual way to prepare ketones is to use the addition of aldehydes and organometallic reagents such as Grignard reagents to first obtain alcohols, and then oxidize them with oxidants to obtain ketones. This preparation method has long steps and requires equivalent oxidants. Therefore, atoms are not economical.

Method used

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  • Polycyclic ketone preparation method
  • Polycyclic ketone preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Take a dry Sis reaction tube, weigh into Cu(OAc) 2 (4.5mg, 0.025mmol), potassium carbonate (35.0mg, 0.25mmol), diethyl azodicarboxylate (8.7mg, 0.050mmol), and the ligand pentamethyldiethylenetriamine (8.7mg, 0.050 mmol), vacuumize and change nitrogen, replace three times, then add structural formula such as 2-ethynyl benzaldehyde (32.5mg, 0.25mmol) shown in 1a and structural formula such as 2-allyl-2 bromomalonic acid shown in 2a Diethyl ester (83.4 mg, 0.30 mmol) in 3 mL of acetonitrile was reacted under reflux at 80°C for 10 h, cooled to room temperature, quenched with 10 mL of water, extracted three times with ethyl acetate (10 mL), combined and washed with saturated drinking water. phase, dried over anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel (300-400 mesh) column chromatography (eluent: petroleum ether / ethyl acetate volume ratio: 10 / 1) to obtain 63 mg of colorless oily product 3aa, yield 86%. 1 H NMR (400MHz, CDCl 3 ...

Embodiment 2

[0031] Except that enyneal represented by structural formula 1b was used instead of enyneal represented by structural formula 1a in Example 1, the rest of the operation steps were the same as in Example 1. Yield: 76%, colorless liquid. 1 H NMR (600MHz, CDCl 3 )δ1.27(m,6H),2.12(dd,J=8.4,13.3Hz,1H),2.49(dd,J=13.9,15.8Hz,1H),2.90-3.10(m,2H),3.42-3.59 (m,1H),3.91(s,3H),4.13-4.26(m,3H),6.48(d,J=2.3Hz,1H),7.72-7.80(m,1H),8.14-8.18(m,1H ),8.58-8.61(m,1H); 13 C NMR (151MHz, CDCl 3 )δ13.9, 13.9, 39.1, 42.0, 45.3, 52.2, 61.8, 61.9, 66.3, 125.0, 125.7, 128.8, 130.5, 130.9, 133.9, 138.6, 142.8, 165.8, 169.5, 170.5, 195.8; for C 21 h 23 o 7 (M+H) + 387.1444,found 387.1437.

[0032] The reaction formula is as follows:

[0033]

Embodiment 3

[0035] Except that enyneal represented by structural formula 1c is used instead of enyneal represented by structural formula 1a in Example 1, the rest of the operation steps are the same as in Example 1, yield: 75%, white solid, melting point: 97-99°C; 1 H NMR (600MHz, CDCl 3 )δ1.32(dt, J=7.1, 14.4Hz, 6H), 2.18(dd, J=8.3, 13.3Hz, 1H), 2.54(dd, J=13.9, 15.9Hz, 1H), 3.10(m, 2H ), 3.57(tdd, J=2.5, 8.0, 13.8Hz, 1H), 4.26(m, 4H), 6.52(d, J=2.4Hz, 1H), 7.82(dt, J=4.9, 8.3Hz, 2H) ,8.31(s,1H); 13 C NMR (151MHz, CDCl 3 )δ14.0, 14.0, 39.1, 42.1, 45.3, 62.0, 62.0, 66.4, 123.5 (q, J = 272.7Hz), 124.7 (q, J = 3.9Hz), 125.2, 126.3, 129.8 (q, J = 3.4 Hz), 131.1 (q, J=3.4Hz), 131.2, 138.0, 142.4, 169.6, 170.6, 195.5. 19 F NMR (565MHz, CDCl 3 )δ-63.00(s,1H); HRMS(APCI) calcd for C 20 h 20 f 3 o 5 (M+H) + 397.1263,found 397.1255.

[0036] The reaction formula is as follows:

[0037]

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Abstract

The invention discloses a polycyclic ketone preparation method. The method comprises that in the presence of a copper catalyst, a nitrogen ligand, a reducer and an alkali, enyne aldehyde and alpha-bromo unsaturated carbonyl compound are stirred in a solvent and undergo a reaction at a temperature of 80 DEG C for 10h and the reaction product is treated to form polycyclic ketone. The method can be operated simply and has one process, good function group compatibility, wide substrate applicability and a good yield. The method can form six novel C-C bonds and four carbon rings through one process and has high efficiency and step economy.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a preparation method of polycyclic ketones. Background technique [0002] Ketones are a very common organic structural unit, widely found in many biologically active natural products or drugs. For example, cortisone (Cortisone), an adrenocortical hormone drug that can be used to treat rheumatism, rheumatoid arthritis, and allergic dermatitis, prednisone (Prednisone) that has anti-inflammatory and anti-allergic effects, and antibacterial and cardiotonic The active Halenaquinone and the like all have the structure of polycyclic ketones, as shown below: [0003] [0004] Usually, the method of preparing ketones is to use the addition of aldehydes and organometallic reagents such as Grignard reagents to obtain alcohols first, and then oxidize them with oxidants to obtain ketones. It can be seen that it is of great significance to develop a one-step method for the dir...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/347C07C69/757C07C69/76C07C45/72C07C49/675C07J11/00
CPCC07C45/72C07C49/675C07C67/347C07C69/757C07C69/76C07J11/00
Inventor 朱钢国车超黄倩雯郑汉良
Owner ZHEJIANG NORMAL UNIVERSITY
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