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A method for synthesis of medium-ring compounds of 9 to 12 rings

A technology for cyclic compounds and iodides, applied in the field of synthesizing 9-12-membered mid-ring compounds, can solve the problems of reduced yield, high production cost, strict operation requirements, etc., and achieves easy separation and purification, strong substrate universality, and reaction simple conditional effect

Inactive Publication Date: 2009-10-07
ZHEJIANG UNIV
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

These traditional synthetic methods require the use of highly diluted or relatively harsh reaction conditions, which not only require strict operation and high production costs, but are mostly limited to the preparation of eight-membered ring products. When preparing larger cyclic compounds, such as 9-12 The yield will be greatly reduced when the membered ring compound is used, therefore, there are still many limitations in practical application

Method used

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  • A method for synthesis of medium-ring compounds of 9 to 12 rings
  • A method for synthesis of medium-ring compounds of 9 to 12 rings
  • A method for synthesis of medium-ring compounds of 9 to 12 rings

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020]

[0021] Potassium carbonate (55.6mg, 0.4mmol) was added to the reaction tube, the nitrogen was replaced three times, and tetrakis(triphenylphosphine)palladium (5.7mg, 0.005mmol), 3-(2-(2, 2-Bis(methoxycarbonyl)-4,5-dihexenyl)phenyl)-2-(methoxycarbonyl)propanoic acid methyl ester 1a (41.8mg, 0.1mmol), iodobenzene (40.9mg, 0.2mmol ), and N,N-dimethylacetamide (1.5 mL). After reacting at 80°C for 11 hours, the reaction was first quenched with 10 mL of water, and then extracted with ether (30 mL×3). The ether layers were combined, washed with water and brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying, and silica gel column separation (petroleum ether / ethyl acetate / dichloromethane=5 / 1 / 1) to obtain the product (E)-8-phenyl-6,6,11,11-(tetramethoxy Carbonyl)benzo-8-cyclodecene (44.9 mg, 91%) 2a. The product is a white solid, melting point; 204-205°C (dichloromethane / n-hexane).

[0022] 1 H NMR (300MHz, CDCl 3 )δ7.34-7.18(m, 5H), 7.18-7.08(m, 2H),...

Embodiment 2

[0024]

[0025] According to the method described in Example 1, potassium carbonate (110.3mg, 0.8mmol), tetrakis (triphenylphosphine) palladium (11.6mg, 0.01mmol), 1a (83.0mg, 0.2mmol), p-methoxycarbonyl iodobenzene (103.9mg, 0.4mmol) was reacted in N,N-dimethylacetamide (3mL) to give product 2b (92.0mg, 84%) as a white solid with a melting point of 201-202°C (dichloromethane / n-hexane) .

[0026] 1 H NMR (300MHz, CDCl 3 )δ7.95(d, J=8.3Hz, 2H), 7.30(d, J=8.3Hz, 2H), 7.18-7.09(m, 2H), 6.91-6.78(m, 2H), 5.23(dd, J =13.5Hz, J=4.7Hz, 1H), 3.90(s, 3H), 3.87(s, 3H), 3.84(s, 3H), 3.80(s, 3H), 3.58(d, J=14.7Hz, 1H ), 3.45(d, J=15.0Hz, 1H), 3.26(d, J=14.4Hz, 1H), 3.17(d, J=14.7Hz, 2H), 2.96(d, J=15.0Hz, 1H), 2.87(s, 3H), 2.63(dd, J=13.5Hz, J=3.9Hz, 1H), 2.45(t, J=13.5Hz, 1H); 13 C NMR (75MHz, CDCl 3 ): δ172.0, 171.7, 171.1, 170.7, 166.7, 147.1, 139.5, 135.4, 135.2, 130.9, 129.8, 129.4, 129.1, 128.8, 127.6, 127.1, 127.0, 58.5, 57.8, 52.8, 52.5, 2 51.8, 33.1, 32.4, 31.0, 30.3; I...

Embodiment 3

[0028]

[0029] According to the method described in Example 1, potassium carbonate (109.6mg, 0.8mmol), tetrakis (triphenylphosphine) palladium (11.4mg, 0.01mmol), 1a (82.8mg, 0.2mmol), 4-acetyl iodobenzene (98.4mg, 0.4mmol) was reacted in N,N-dimethylacetamide (3mL) to give product 2c (94.3mg, 89%) as a white solid, melting point: 156-158°C (dichloromethane / n-hexane) .

[0030] 1 H NMR (300MHz, CDCl 3)δ7.87(d, J=7.8Hz, 2H), 7.31(d, J=7.8Hz, 2H), 7.17-7.05(m, 2H), 6.90-6.76(m, 2H), 5.24(dd, J =13.0Hz, J=4.2Hz, 1H), 3.86(s, 3H), 3.83(s, 3H), 3.79(s, 3H), 3.57(d, J=14.7Hz, 1H), 3.44(d, J =15.0Hz, 1H), 3.25(d, J=14.7Hz, 1H), 3.16(d, J=14.7Hz, 2H), 2.96(d, J=14.7Hz, 1H), 2.86(s, 3H), 2.68-2.55(m, 4H), 2.44(t, J=13.0Hz, 1H); 13 C NMR (75MHz, CDCl 3 ): δ197.5, 171.9, 171.6, 171.1, 170.7, 147.3, 139.4, 135.7, 135.3, 135.2, 131.0, 129.8, 129.4, 127.84, 127.76, 127.1, 127.0, 58.5, 57.8, 55.8, 65. 33.1, 32.4, 30.9, 30.2, 26.6; IR (KBr, cm -1 ): 3036, 3003, 2955, 2845, 1733, 1...

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Abstract

A method for high stereo and regioselective synthesis of medium-ring compounds of 9 to 12 rings. The product is prepared by the reaction of allenes with nucleophilic group substitution at terminal with aryl iodides or alkenyl iodides, and then mixing at 80 DEG C under the condition of taking four (triphenylphosphine) palladium chloride as catalyst, potassium carbonate as alkali, N, N-dimethyl acetamide as solvent. The invention of simple operation, high area and stereoselectivity of the reaction, easy obtained raw material and reagent, easy separation and purification products, and no need ofusing a high degree of dilution reaction conditions, which is suitable for synthesis of medium-ring compounds of 9 to 12 rings.

Description

technical field [0001] The invention relates to a method for synthesizing 9- to 12-membered mesocyclic compounds, that is, through the reaction of allenes substituted with nucleophilic groups at the end and aryl iodides or alkenyl iodides, the corresponding mesocyclic compounds are synthesized with high regioselectivity and stereoselectivity compound method. Background technique [0002] Mesocyclic compounds widely exist in natural products and have certain physiological activities. They have great development and utilization value in the field of biotechnology, medicine and pesticides. Reported in the literature by carbon-carbon bond formation to build ring product mainly adopts RCM reaction (Chem.Rev., 2004,104,2199; Chem.Rev., 2004,104,2239), the cyclization reaction (Acc .Chem.Res., 1998, 31, 603) and cyclization reactions involving other metals such as palladium (Heterocycles, 2007, 71, 1011; Chem.Rev.2007, 107, 239). These traditional synthetic methods require the us...

Claims

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Application Information

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IPC IPC(8): C07B37/10C07C69/753C07C69/757C07C67/343C07C67/313C07C67/307C07D213/55C07D225/06B01J31/24
Inventor 姜昕鹏麻生明傅春玲杨青
Owner ZHEJIANG UNIV
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