Synthetic method of beta, beta-disubstituted propionate derivative

A synthesis method and technology of propionate, applied in the beta field, can solve the problems of narrow substrate range, poor functional group tolerance, inability to obtain diverse structures, etc., to achieve the effects of easy reaction, reduction of synthesis steps, and rich applicability

Active Publication Date: 2020-02-04
NANJING TECH UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0011] This method requires the use of aryl lithium reagents, which makes the functional group tolerance of the substrate poor, and the scope of the substrate is narrow, and it is impossible to obtain β, β-disubstituted propionate derivatives with various structures

Method used

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  • Synthetic method of beta, beta-disubstituted propionate derivative
  • Synthetic method of beta, beta-disubstituted propionate derivative
  • Synthetic method of beta, beta-disubstituted propionate derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] Example 1 At 25°C, in a glove box under an argon atmosphere, three (dibenzylidene indeneacetone) dipalladium Pd 2 (dba) 3 (4.6mg, 0.005mmol), 1,3-bis(2,6-diisopropylphenyl) imidazolium chloride (6.3mg, 0.015mmol), α,α,α-terpyridine (2.3mg, 0.01 mmol), THF (2 mL) was added to an oven-dried microwave tube (10 mL). Next iodobenzene (0.2 mmol) was added and the solution turned from brown to green. Subsequently, MeOH (100 uL), cinnamaldehyde (0.1 mmol), KOtBu (16.8 mg, 0.15 mmol) were gradually added to the mixture (after adding KOtBu, the reaction solution changed from green to gray). Seal the microwave tube with an aluminum cap fitted with a rubber septum and remove it from the glove box. Stir at room temperature 25°C for 12 hours. The cap was removed, the reaction mixture was exposed to the air, and filtered through a silica gel column (rinsed with 5 mL of ethyl acetate) to obtain a dark brown solution. Volatile materials were removed using a rotary evaporator. The ...

Embodiment 2

[0051] Example 2 Use 4-tert-butyl iodobenzene (52.0mg, 0.2mmol) to replace the iodobenzene in Example 1, the remaining operations are the same as in Example 1, and the crude product is purified by flash column chromatography (petroleum ether: ethyl acetate = 100:1), to obtain the corresponding colorless oil product 2 (20.1mg, 68% yield), the proton spectrum and carbon spectrum nuclear magnetic resonance spectrum of the product are respectively as follows Figure 2A and Figure 2B As shown, the spectrogram data is: 1 H NMR (400MHz, CDCl 3 )δ7.30–7.22(m,6H),7.20–7.12(m,3H),4.52(t,J=8.0Hz,1H),3.57(s,3H),3.05(d,J=8.0Hz,2H ),1.27(s,9H)ppm; 13 C{ 1 H}NMR (101MHz, CDCl 3 )δ172.5, 149.3, 143.7, 140.5, 128.6, 127.8, 127.3, 126.6, 125.6, 51.8, 46.6, 40.7, 34.5, 31.4ppm.

Embodiment 3

[0052] Example 3 Use 4-methoxy iodobenzene (46.8mg, 0.2mmol) to replace the iodobenzene in Example 1, the rest of the operations are the same as in Example 1, and the crude product is purified by flash column chromatography (petroleum ether: ethyl acetate = 70:1), to obtain the corresponding colorless oil product 3 (17.5mg, 65% yield), the proton spectrum and carbon spectrum nuclear magnetic resonance spectrum of the product are respectively as follows Figure 3A and Figure 3B As shown, the spectrogram data is: 1 H NMR (400MHz, CDCl 3 )δ7.30–7.25(m,2H),7.23–7.12(m,5H),6.87–6.73(m,2H),4.50(t,J=8.0Hz,1H),3.75(s,3H),3.57 (s,3H),3.02(d,J=8.0Hz,2H)ppm; 13 C{ 1 H}NMR (101MHz, CDCl 3 )δ171.3, 157.1, 142.8, 134.6, 127.6, 127.5, 126.5, 125.4, 112.9, 54.2, 50.6, 45.1, 39.7ppm.

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Abstract

The invention discloses a synthetic method of beta, beta-disubstituted propionate derivative, and belongs to the field of organic synthesis. An aldehyde compound, an iodide and an alcohol are adoptedto synthesize the beta, beta-disubstituted propionate derivative through a one-pot method, and the synthetic method is used for realizing beta-bit arylation and esterification of carbonyl groups of alpha, beta-unsaturated aldehyde to synthesize beta, beta-disubstituted methyl propionate. The synthesis steps of a traditional method are reduced, the reaction yield is increased, and according to thesynthetic method, raw materials are cheap, the operation steps are simple, the reaction condition is mild, and applicability of reaction substrates is greatly enriched.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to a method for synthesizing β, β-disubstituted propionate derivatives. Background technique [0002] β, β-disubstituted propionate derivatives are important organic raw materials and chemical products with various physiological activities. As intermediates of pharmaceuticals, pesticides, dyes, spices and other fine chemical products, β, β-disubstituted propionate derivatives are widely used, so their synthesis has always been one of the important contents in the global chemical field. At present, many methods have been developed to synthesize this kind, but these methods all have their own shortcomings, such as the need for multi-step reactions, the difficulty of obtaining the substrates required for synthesis, and harsh reaction conditions. The synthesis of corresponding similar target product compounds has been reported in recent years, mainly as follows: [0003] The first one...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/12C07C67/00C07C69/616C07C69/65C07C69/734C07C69/76C07C69/732C07C227/02C07C229/42C07C253/30C07C255/57C07D333/24C07D333/60C07D307/54C07D307/79C07D215/12
CPCC07B41/12C07C67/00C07C227/02C07C253/30C07D215/12C07D307/54C07D307/79C07D333/24C07D333/60C07C69/616C07C69/65C07C69/734C07C69/76C07C229/42C07C69/732C07C255/57
Inventor 毛建友凌搏杨文军
Owner NANJING TECH UNIV
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