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New green synthesis method for efficient synthesis of isoquinoline derivatives by transition metal catalyzed C-H activation/cyclization reaction

A technology of transition metal catalysis and cyclization reaction, applied in the direction of organic chemistry, can solve the problems of lengthy steps, environmental pollution, high cost, etc., and achieve the effect of simple steps and broad application prospects

Inactive Publication Date: 2019-04-12
SICHUAN UNIV
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Problems solved by technology

[0003] The present invention realizes a new synthesis method of constructing isoquinoline and its derivatives through transition metal-catalyzed C-H activation one-step coupling and cyclization using water as solvent and sulfur ylide as carbene donor, which solves the problem of lengthy steps in traditional synthesis methods. Harsh reaction conditions, low atom utilization, environmental pollution caused by the use of toxic organic solvents, high cost, etc.

Method used

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  • New green synthesis method for efficient synthesis of isoquinoline derivatives by transition metal catalyzed C-H activation/cyclization reaction
  • New green synthesis method for efficient synthesis of isoquinoline derivatives by transition metal catalyzed C-H activation/cyclization reaction
  • New green synthesis method for efficient synthesis of isoquinoline derivatives by transition metal catalyzed C-H activation/cyclization reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Implementation Example 1: Synthesis of Compound 1

[0022]

[0023] (1) In a clean reactor, add benzylamine (21.4 mg, 0.2 mmol), 2,6-dimethoxyphenylthioylide (102.5 mg, 0.4 mmol), dichloro(pentamethylcyclopentadiene) Alkenyl) rhodium (III) dimer (6.18 mg, 0.01 mmol), silver acetate (6.67 mg, 0.04 mmol) and water (2 mL), put in an oil bath at 100°C and stir for 24 h.

[0024] (2) After the reaction, dichloromethane was added for extraction, the dichloromethane layer was collected, the solvent was removed under reduced pressure, and the residue was separated and purified by silica gel column chromatography to obtain a white solid with a yield of 75%. 1 H NMR (400 MHz, CDCL 3 ) δ 9.39 (s,1H), 8.00 (d, J = 8.1 Hz, 1H), 7.83 (d, J = 8.2 Hz, 1H), 7.71 (s, 1H), 7.67(t, J = 7.6 Hz, 1H), 7.58 (t, J = 7.4 Hz, 1H), 7.35 (t, J = 8.4 Hz, 1H), 6.69(d, J = 8.4 Hz, 2H), 3.73 (s, 6H). 13 C NMR (101 MHz, CDCl 3 ) δ 157.25(s,2 C ), 150.79, 146.38, 135.22, 129.02, 128.5...

Embodiment 2

[0025] Implementation Example 2: Synthesis of Compound 2

[0026]

[0027] (1) Add p-bromobenzylamine (37.2 mg, 0.2 mmol), 2,6-dimethoxyphenylthioylide (102.5 mg, 0.4 mmol), dichloro(pentamethylcyclo Pentadienyl) rhodium (III) dimer (6.18 mg, 0.01 mmol), silver acetate (6.67 mg, 0.04 mmol) and water (2 mL), put in an oil bath at 100°C and stir for 24 h.

[0028] (2) After the reaction, dichloromethane was added for extraction, the dichloromethane layer was collected, the solvent was removed under reduced pressure, and the residue was separated and purified by silica gel column chromatography to obtain a white solid with a yield of 71.1%. 1 H NMR (400 MHz, CDCl 3 ) δ 9.34 (s,1H), 7.99 (d, J = 1.6 Hz, 1H), 7.86 (d, J = 8.8 Hz, 1H), 7.65 (dd, J = 8.8,1.6 Hz, 1H), 7.61 (s, 1H), 7.35 (t, J = 8.4 Hz, 1H), 6.68 (d, J = 8.4 Hz,2H), 3.73 (s, 6H). 13 C NMR (101 MHz, CDCl 3 ) δ 158.22 (s,2 C), 151.72 (s), 148.65 (s), 137.30 (s), 130.50 (s), 129.89 (s), 129.19 (s), 128.9...

Embodiment 3

[0029] Implementation Example 3: Synthesis of Compound 3

[0030]

[0031] (1) Add p-methylbenzylamine (24.2 mg, 0.2 mmol), 2,6-dimethoxyphenylthioylide (102.5 mg, 0.4 mmol), dichloro(pentamethyl Cyclopentadienyl) rhodium (III) dimer (6.18 mg, 0.01 mmol), silver acetate (6.67 mg, 0.04 mmol) and water (2 mL), were placed in an oil bath at 100°C and stirred for 24 h.

[0032] (2) After the reaction, dichloromethane was added for extraction, the dichloromethane layer was collected, the solvent was removed under reduced pressure, and the residue was separated and purified by silica gel column chromatography to obtain a light yellow solid with a yield of 56.4%. 1 H NMR (400 MHz, CDCl 3 ) δ 9.31 (s,1H), 7.89 (d, J = 8.4 Hz, 1H), 7.60 (d, J = 9.7 Hz, 2H), 7.42 (dd, J = 8.4,1.2 Hz, 1H), 7.34 (t, J = 8.4 Hz, 1H), 6.68 (d, J = 8.4 Hz, 2H), 3.73 (s,6H), 2.54 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 157.26 (s,2 C ), 150.32 (s), 146.29 (s), 139.35 (s), 135.55 (s), 128.50 (s...

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Abstract

The invention relates to a new green synthesis method for efficient formation of a C-C bond on an aromatic (heterocyclic) ring and cyclization into isoquinoline derivatives by transition metal catalyzed C-H activation / cyclization reaction and use of water as a solvent and sulfur ylide as a carbene donor. Compared with the traditional method, the method provided by the invention has the characteristics of easily available raw materials, simple steps and no use of toxic organic solvent, is a mild, rapid, simple, effective and environment-friendly method for preparation of isoquinoline mother ring, and has broad application prospects.

Description

technical field [0001] The invention relates to a new green synthesis method for efficiently forming a C-C bond on an aromatic (hetero) ring and synthesizing isoquinoline derivatives by using water as a solvent, sulfur ylide as a carbene donor, and transition metal-catalyzed C-H activation / cyclization reaction method. Background technique [0002] Isoquinoline and its derivatives are a common parent ring structure of organic compounds, which are widely found in many drugs and natural compounds 1-5 and organic materials 6, 7 . Traditional methods for the synthesis of isoquinolines and their derivatives include the Pomeranz-Fritsch reaction 8 , Bischler-Napieralski reaction 9 React with Pictet-Spengler 10 , These reactions generally have the following disadvantages: cumbersome steps, harsh conditions, low yield, poor applicability of functional groups, etc. In recent years, C-H activation has achieved rapid development in the field of organic synthesis. A variety of comp...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D217/16
CPCC07D217/16
Inventor 吴勇海俐王乾韬管枚赖睿智
Owner SICHUAN UNIV
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