Chiral dicyclic compound and asymmetric syntheses method thereof

A synthesis method and compound technology, which are applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve the problems of restricting the rapid development of chiral bicyclic diene compounds, and achieve good reaction characteristics and simple reaction operations. , the effect of mild reaction conditions

Active Publication Date: 2012-07-04
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, complex synthetic methods limit the rapid development of chiral bicyclodiene compounds as chiral ligands (Angew.Chem.Int.Ed.2008, 47, 4482)

Method used

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  • Chiral dicyclic compound and asymmetric syntheses method thereof
  • Chiral dicyclic compound and asymmetric syntheses method thereof
  • Chiral dicyclic compound and asymmetric syntheses method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0073] Example 1: (1S, 4S, 5S, 6R) 6-(2-methoxystyryl)-5-nitrobicyclo[2,2,2]octan-2-one

[0074] Add 2-methoxystyryl nitroalkene (0.102g, 0.5mmol), cyclohexenone (0.192g, 2mmol) and 1mL chloroform in the 25mL test tube, in the chiral secondary amine catalyst (IV) (0.02g, 0.1mmol), PPG1000 (0.3g, 0.3mmol) and benzoic acid (0.012g, 0.1mmol) were jointly catalyzed and reacted at 25°C for 36h, extracted with ethyl acetate (3×20mL), and after distillation to remove the solvent, use Diethyl ether-petroleum ether system is used as eluent (diethyl ether volume content is 20%), 100-200 mesh column chromatography silica gel is used as filler, column chromatography is separated and purified to obtain the target compound (0.102g, yield 68%, appearance / Endotype (exo / endo) > 20:1, Ee value is 90%), where 1 H NMR (500MHz, CDCl 3 ): δ=7.334-7.309 (m, 1H), 7.234-7.207 (m, 1H), 6.906-6.813 (m, 2H), 6.476-6.444 (m, 1H), 6.014-5.944 (m, 1H), 4.622 -4.613(m, 1H), 3.829(s, 3H), 3.750-3.703(m, ...

Embodiment 2

[0075] Example 2: Preparation of (1S, 4S, 5S, 6R) 6-(4-methoxystyryl)-5-nitrobicyclo[2,2,2]octan-2-one

[0076] Add 4-methoxystyryl nitroalkene (0.102g, 0.5mmol), cyclohexenone (0.192g, 2mmol) and 1mL chloroform in a 25mL test tube, in the chiral secondary amine catalyst (IV) (0.02g, 0.1mmol), PPG1000 (0.3g, 0.3mmol) and benzoic acid (0.012g, 0.1mmol) were jointly catalyzed and reacted at 25°C for 36h, extracted with ethyl acetate (3×20mL), and after distillation to remove the solvent, use Diethyl ether-petroleum ether system is used as eluent (diethyl ether volume content is 20%), 100-200 mesh column chromatography silica gel is used as filler, and column chromatography is separated and purified to obtain the target compound (0.123g, yield 66%, appearance / Endotype (exo / endo) > 20:1, Ee value 94%), where 1 H NMR (500MHz, CDCl 3 ): δ=7.261-7.238 (m, 2H), 6.837-6.820 (m, 2H), 6.462-6.430 (m, 1H), 5.842-5.795 (m, 1H), 4.564-4.554 (m, 1H), 3.791 (s, 3H), 3.697-3.671(m, 1H), 2...

Embodiment 3

[0077] Example 3: Preparation of (1S, 4S, 5S, 6R) 6-(4-methylstyryl)-5-nitrobicyclo[2,2,2]octan-2-one

[0078] Add 4-methylstyryl nitroalkene (0.094g, 0.5mmol), cyclohexenone (0.192g, 2mmol) and 1mL chloroform in the 25mL test tube, in chiral secondary amine catalyst (IV) (0.02g, 0.1 mmol), PPG1000 (0.3g, 0.3mmol) and benzoic acid (0.012g, 0.1mmol) under the co-catalysis of 25 ℃ for 36h, extracted with ethyl acetate (3 × 20mL), after distilling off the solvent, using diethyl ether -petroleum ether system is the eluent (ether volume content is 20%), 100-200 mesh column chromatography silica gel is used as filler, column chromatography is separated and purified to obtain the target compound (0.090g, yield 64%, exo / internal Type (exo / endo) > 20:1, Ee value is 86%), where 1 H NMR (500MHz, CDCl 3 ): δ=7.213-7.197(d, J=8Hz, 2H), 7.108-7.092(d, J=8Hz, 2H), 6.488-6.456(d, J=16Hz, 1H), 5.933-5.886(m, 1H ), 4.566-4.555(m, 1H), 3.710-3.684(m, 1H), 2.945-2.928(m, 1H), 2.568-2.551(m, 1H...

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Abstract

The invention discloses a chiral dicyclic compound and an asymmetric syntheses method thereof, and the chiral dicyclic compound has a structure as shown in formula (I). According to the invention, a cyclohexenone derivative with a structure as shown in formula (II) and a nitroalkene derivative with a structure as shown in formula (III) are used as substrates, and a reaction is performed in an organic solvent with the catalysis of a chiral secondary amine catalyst, a polyglycol-series compound and an acid so as to obtain the chiral dicyclic compound with a structure as shown in formula (I). The chiral dicyclic compound synthesized in the invention has chirality, can be used as a synthetic intermediate of chiral compounds, and has wide application prospects.

Description

(1) Technical field [0001] The invention relates to a chiral bicyclic compound and an asymmetric synthesis method thereof. (2) Background technology [0002] Chirality is a fundamental property of nature and one of the most important properties of living systems. Proteins, nucleic acids, and polysaccharides, which are the three major material bases of living bodies, almost all exist in a single configuration in living bodies. For living organisms, the enantiomers of many chiral compounds have completely different physiological activities, so the synthesis of optically active organic compounds is a challenging task for chemists, and it is also one of the hottest research topics in recent years . Undoubtedly, asymmetric synthesis is the most effective way to prepare chiral compounds, and catalytic asymmetric synthesis is the most ideal asymmetric synthesis method. It can obtain a large number of chiral products with only a small amount of chiral catalyst, which is the develo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C205/46C07C201/12
Inventor 许丹倩夏爱宝徐振元
Owner ZHEJIANG UNIV OF TECH
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