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High-effective synthesis of dihydrofuran derivative through Lewis acid catalyzed insertion reaction

A technology of furan derivatives and insertion reaction, applied in the direction of organic chemistry, can solve the problems of lengthy steps, use of toxic organic solvents, poor substrate compatibility, etc., and achieve the effect of simple steps and broad application prospects

Active Publication Date: 2020-03-31
SICHUAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

It solves the problems of long steps, poor substrate compatibility, low atom utilization, use of toxic organic solvents, environmental pollution, and high cost in traditional synthetic methods

Method used

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  • High-effective synthesis of dihydrofuran derivative through Lewis acid catalyzed insertion reaction
  • High-effective synthesis of dihydrofuran derivative through Lewis acid catalyzed insertion reaction
  • High-effective synthesis of dihydrofuran derivative through Lewis acid catalyzed insertion reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment example 1

[0014] Implementation Case 1: Synthesis of Compound 1

[0015]

[0016] Add enynone (38.4 mg, 0.2 mmol), phenylsulfide ylide (98 mg, 0.50 mmol), zinc chloride (1.3 mg, 0.1 mmol) and [BMIM]NTf in a clean reactor successively. 2 Ionic liquid (2 mL), put in a pot at room temperature and stir overnight. After the reaction, it was separated and purified directly by silica gel column chromatography to obtain a yellow oil with a yield of 85%. 1 H NMR (400MHz, CDCl 3 ) δ 8.16 – 8.01 (m, 2H), 7.65 (t, J = 7.2 Hz, 1H), 7.53 (t, J = 8.0Hz, 2H), 5.78 (d, J = 6.0 Hz, 1H), 4.28 (dd, J = 5.6, 1.2 Hz, 1H), 2.32 (d, J = 0.8 Hz, 3H), 2.27 (s, 3H), 1.25 (s, 9H); 13 C NMR (151 MHz, Chloroform-d) δ194.6, 193.0, 168.4, 134.5, 133.8, 129.5, 129.2, 113.0, 92.9, 87.8, 77.9,38.1, 31.3, 29.8, 27.8, 15.2): HRMS ( m / z Calculated value C 20 h 23 o 3 : [M+H + ] 311.1642; found 311.1641.

Embodiment example 2

[0017] Implementation Case 2: Synthesis of Compound 2

[0018]

[0019] Add enynone (38.4 mg, 0.2 mmol), 4-methylphenylsulfide ylide (105 mg, 0.50 mmol), zinc chloride (1.3 mg, 0.1 mmol) and [BMIM]NTf to a clean reactor successively. 2 Ionic liquid (2 mL), put in a pot at room temperature and stir overnight.

[0020] After the reaction, it was separated and purified directly by silica gel column chromatography to obtain a yellow oil with a yield of 82%. 1 H NMR (400 MHz, Chloroform- d ) δ 7.98 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 5.76 (d, J = 6.0 Hz, 1H), 4.24 (d, J = 5.6 Hz, 1H), 2.44 (s, 3H), 2.31 (s,3H), 2.26 (s, 3H), 1.24 (s, 9H); 13 C NMR (101 MHz, Chloroform-d) δ 193.3,191.3, 167.1, 144.3, 129.9, 128.5, 128.3, 111.6, 91.4, 86.4, 76.7, 36.8,30.0, 28.5, 26.5, 20.8, 13.9: HRMSI; m / z Calculated value C 21 h 25 o 3 : [M+H + ] 325.1798; found 325.1798.

Embodiment example 3

[0021] Implementation Case 3: Synthesis of Compound 3

[0022]

[0023] Add enynone (38.4 mg, 0.2 mmol), 4-methoxyphenylthioylide (113 mg, 0.50 mmol), brominated ketone (2.23 mg, 0.1 mmol), [BMIM] NTf 2 Ionic liquid (2 mL), put in a pot at room temperature and stir overnight. After the reaction, it was directly separated and purified by silica gel column chromatography to obtain a yellow oil with a yield of 69%. 1 HNMR (400 MHz, CDCL 3 ) δ 8.07 (d, J = 8.8 Hz, 2H), 6.98 (d, J = 8.8 Hz, 2H), 5.74 (d, J = 6.0 Hz, 1H), 4.27 (d, J = 6.0 Hz, 1H), 3.90 (s, 3H), 2.31 (s,3H), 2.27 (s, 3H), 1.24 (s, 9H); 13 C NMR (101 MHz, Chloroform- d ) δ 193.3, 190.2, 167.0, 163.4, 130.6, 125.6, 113.1, 111.7, 91.5, 86.4, 76.8, 54.6, 36.8, 30.0, 28.5 26.5, 13.9; HRMS (ESI): m / z Calculated value C 21 h 25 o 4 : [M+H + ] 341.1753; found 341.1752.

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Abstract

The invention relates to a new synthesis method of a dihydrofuran derivative through a Lewis acid catalyzed insertion reaction to high-effectively form a C-C bond and cyclization with an ionic liquidbeing a solvent and sulfur ylide being a nucleophilic reagent. Compared with other methods, the method of the invention employs feasible raw materials and is simple in steps, avoids use of toxic organic solvent, is a gentle, quick, simple, effective and environment-friendly method of preparing a dihydrofuran parent ring. The method has extensive application prospect.

Description

technical field [0001] The invention relates to a new synthetic method for forming a C-C bond and cyclosynthesizing dihydrofuran derivatives with ionic liquid as a solvent, sulfur ylide as a nucleophile, Lewis acid-catalyzed insertion reaction, and belongs to the field of chemical synthesis. Background technique [0002] Furan and its derivatives are a common parent ring structure of organic compounds, which widely exist in a variety of drugs and natural compounds 1-4 . The traditional methods for synthesizing furan and its derivatives include Pall-Knorr Furan synthesis reaction, Nickl Benzofuran Synthesis reaction, etc. These reactions have the disadvantages of cumbersome steps, harsh conditions, low yield, and poor applicability of functional groups. In recent years, enyne ketone compounds have achieved rapid development in the field of organic synthesis, which can form carbene bodies under the catalysis of metals, respectively, with alkenes 5 , Diazo compounds 6-7 , su...

Claims

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Application Information

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IPC IPC(8): C07D307/28
CPCC07D307/28Y02P20/54
Inventor 吴勇海俐管玫罗意
Owner SICHUAN UNIV
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