CN117384177A - Synthesis method of chiral pyrrole bridged ring compound - Google Patents

Synthesis method of chiral pyrrole bridged ring compound Download PDF

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CN117384177A
CN117384177A CN202311327144.3A CN202311327144A CN117384177A CN 117384177 A CN117384177 A CN 117384177A CN 202311327144 A CN202311327144 A CN 202311327144A CN 117384177 A CN117384177 A CN 117384177A
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compound
bridged ring
chiral
pyrrole
copper
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孔端阳
罗赛莉
马月
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The invention discloses a method for chiral pyrrole bridged ring compounds, which comprises the following steps: in an organic solvent, catalyzing by a copper catalysis system or a silver catalysis system, and carrying out asymmetric [3+2] cycloaddition reaction on an imido ester compound I and a butenolide compound II in the presence of cesium carbonate to obtain a chiral pyrrole bridged ring compound III; the copper catalytic system consists of copper salt and chiral ligand, and the chiral ligand has a structure shown in a formula IV; the silver catalytic system consists of silver salt and chiral ligand, and the chiral ligand has a structure shown in a formula V.

Description

Synthesis method of chiral pyrrole bridged ring compound
Technical Field
The invention belongs to the field of organic synthesis, and relates to a method for synthesizing chiral pyrrole bridged ring compounds.
Background
Chiral pyrrole bridged ring compounds are widely used in bioactive natural products, can be used as precursors of a plurality of natural products and drug molecules, and are also important raw materials in the fields of organic synthesis and fine chemical engineering, such as (-) -rhodophycoerythrin. However, such compounds are difficult to obtain only by isolation and biosynthesis in nature, and have disadvantages of low content, high cost, and the like.
Transition metal catalyzed asymmetric carbon-carbon (C-C) bond activation has been a powerful tool for achieving novel complex molecular building and conversion, with the advantage of high step economy, and has become a versatile method for building various cyclic compounds for decades. And through the combination of chiral ligand and metal, the control of a plurality of chiral centers can be completed by one-step reaction, and the asymmetric efficient construction of the core skeleton of the natural product is completed.
Therefore, the development of the intermolecular coupling reaction based on C-C bond activation realized by low-cost metal has potential application value and important methodological significance, but is also challenging to realize the efficient and high-selectivity construction of complex molecules.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide a method for chiral pyrrole bridged ring compounds. The invention takes the transition metal catalyst with simple structure and the chiral ligand which is easy to synthesize as a catalytic system to realize the efficient asymmetric synthesis of chiral pyrrole bridged ring compounds.
The technical scheme of the invention is as follows:
a method for chiral pyrrole bridged ring compounds comprises the following steps:
in an organic solvent, catalyzing by a copper catalysis system or a silver catalysis system, and carrying out asymmetric [3+2] cycloaddition reaction on an imido ester compound I and a butenolide compound II in the presence of cesium carbonate to obtain a chiral pyrrole bridged ring compound III; the copper catalytic system consists of copper salt and chiral ligand IV, wherein the chiral ligand has a structure shown in a formula IV; the silver catalytic system consists of silver salt and chiral ligand V, and the chiral ligand has a structure shown in a formula V;
wherein in the compound I, R 1 Is phenyl, halogenated phenyl and C 1 ～C 8 Alkyl-substituted phenyl, diacetone glucose ester-substituted phenyl, C 1 ～C 8 Alkoxy-substituted phenyl, trifluoromethyl-substituted phenyl, boric acid-substituted phenyl, cyano-substituted phenyl, azaalkyl-substituted phenyl, biphenyl, naphthyl, thienyl, halofuryl, C 1 ～C 8 An alkyl group; r is R 2 Is C 1 ～C 8 Alkyl, C 1 ～C 8 Alkenyl-substituted C 1 ～C 8 Alkyl, silyl; r is R 3 Is hydrogen radical, C 1 ～C 8 An alkyl group;
in the compound II, R 4 Is C 1 ～C 8 Alkyl, C 1 ～C 8 Alkoxy, alkylacyloxy, (hetero) arylacyloxy;
in the compound III, the substituent R 1 、R 2 、R 3 Respectively with R in the compound I 1 、R 2 、R 3 The same; substituent R 4 With R in compound II 4 The same applies.
According to the invention, the solvent is preferably dichloromethane or toluene; the ratio of the volume of the solvent to the mole number of the imido ester compound I is 1mL:0.1mmol; the solvent is anhydrous.
According to a preferred embodiment of the present invention, the copper catalyst is copper triflate; the molar ratio of the copper catalyst to the imido ester compound I is 0.02:0.1; the molar ratio of copper in the copper catalyst to chiral ligand IV is 1:1.
according to the invention, preferably, the silver catalyst is silver acetate; the mol ratio of the silver catalyst to the imido ester compound I is 0.02-0.05: 0.1; the molar ratio of silver to chiral ligand V in the silver catalyst is 1:1.
according to the invention, the molar ratio of cesium carbonate to imido ester compound I is preferably 1:4, a step of; the molar ratio of the compound of formula I to the compound of formula II is 1:2.
according to the invention, the copper catalyst is preferably prepared by the following method: copper salt and chiral ligand IV are added into methylene dichloride under the protection of nitrogen, and stirred for 30 minutes at room temperature, and the obtained solution is a copper catalyst system.
According to the invention, the silver catalyst is prepared by the following method: under the protection of nitrogen, silver salt and chiral ligand V are added into toluene, and stirred for 30 minutes at room temperature, and the obtained solution is a silver catalyst system.
According to the present invention, preferably, the cycloaddition reaction is performed under an inert gas atmosphere, and the inert gas is nitrogen.
According to the invention, the cycloaddition reaction temperature is preferably 0-25 ℃; the cycloaddition reaction time is 2-7 hours.
According to the invention, after the imidic acid ester compound I and the butenolide compound II undergo a [3+2] cycloaddition reaction, the product can be separated and characterized by a conventional separation and purification method. Preferably, the specific post-reaction treatment steps are as follows: spin-drying the reaction solution, separating by silica gel column chromatography to obtain chiral pyrrole bridged ring compound III, wherein the eluent is a mixed solvent of ethyl acetate and petroleum ether, and the volume ratio of the mixed solvent of ethyl acetate and petroleum ether in the mixed solvent is 0.05-0.2: 1.
compared with the prior art, the invention has the beneficial effects that:
the pyrrole bridged ring compound is prepared by taking an imido ester compound I substituted by different substituents and a butenolide compound II substituted by different substituents as raw materials, taking a simple and easily available catalyst with a novel structure and a chiral ligand as a catalytic system, and performing a [3+2] cycloaddition reaction. The method can generate the pyrrole bridged ring compound with high stereoselectivity and regioselectivity, and perform high-efficiency asymmetric synthesis on the pyrrole bridged ring compound.
The catalyst used in the method is a simple and easily available copper catalyst and chiral ligand IV with low price, and the silver catalyst and the chiral ligand with novel structures; the catalyst has the advantages of low cost, high efficiency and the like, and the dosage of the catalyst is small and can be reduced to 2%; the method for preparing the pyrrole bridged ring compound by the [3+2] cycloaddition reaction of the metal catalyst has the advantages of convenient operation, wide substrate application range, low-cost and easily-obtained reaction raw materials and the like.
Detailed Description
The invention is further described below in connection with the specific embodiments, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials, and apparatus, unless otherwise specified, are all commercially available.
The yields described in the examples are molar yields.
The reaction scheme is as follows:
example 1
1a is synthesized as follows:
under nitrogen atmosphere, stirring a dichloromethane solution of copper triflate and (S) -DTBM-SEGPHOS for thirty minutes at room temperature, sequentially adding 1a (38.2 mg,0.2 mmol) and cesium carbonate (16.3 mg,0.05 mmol) and 1b (80 mg,0.4 mmol) into a 4ml reaction bottle, adding a pre-complexed copper catalyst into the reaction bottle, reacting the mixture for 2 hours at room temperature, spinning the reaction solution, separating the mixture by silica gel column chromatography to obtain a target product 1c, eluting with ethyl acetate and petroleum ether (volume ratio is 0.1:1), and obtaining the yield of 93%.
Characterization data for the resulting product 1c are as follows:
white solid (72.7 mg,93% ee)
1 H NMR(400MHz,CDCl 3 )δ:7.50-7.27(m,5H),6.48(s,1H),4.56(d,J＝2.8Hz,1H),4.18(qq,J＝10.4,7.2Hz,2H),3.82(d,J＝7.2Hz,1H),3.37(dt,J＝8.8,3.6Hz,1H),3.34(t,J＝9.2Hz,1H),2.86(br,1H),1.51(s,9H),1.24(t,J＝7.2Hz,3H)ppm.
13 C NMR(100MHz,CDCl 3 )δ:176.2,170.8,150.9,141.0,128.8,128.5,126.5,98.5,84.4,65.0,63.1,61.9,50.8,50.0,27.6,14.1ppm.
Example 2
Under nitrogen atmosphere, stirring a dichloromethane solution of copper triflate and (S) -DTBM-SEGPHOS for thirty minutes at room temperature, sequentially adding 2a (41.8 mg,0.2 mmol) and cesium carbonate (16.3 mg,0.05 mmol) and 1b (80 mg,0.4 mmol) into a 4ml reaction bottle, adding a pre-complexed copper catalyst into the reaction bottle, reacting the mixture for 2 hours at room temperature, spinning the reaction solution, separating the mixture by silica gel column chromatography to obtain a target product 2c, eluting with ethyl acetate and petroleum ether (volume ratio is 0.1:1), and obtaining the yield of 67%.
Characterization data for the resulting product 2c are as follows:
white solid (55 mg,93% ee)
1 H NMR(400MHz,CDCl 3 )δ:7.46-7.00(m,4H),6.49(s,1H),4.54(s,1H),4.21(m,2H),3.82(m,1H),3.33(s,1H),3.32(s,1H),2.84(br,1H),1.51(s,9H),1.27(t,J＝7.2Hz,3H)ppm.
13 C NMR(100MHz,CDCl 3 )δ:176.0,170.6,161.2,150.8,136.9,128.2,128.1,115.7,115.6,98.1,84.5,64.2,63.0,61.9,51.0,49.8,27.6,14.0ppm.
Example 3
Under nitrogen atmosphere, stirring a dichloromethane solution of copper triflate and (S) -DTBM-SEGPHOS for thirty minutes at room temperature, sequentially adding 3a (53.8 mg,0.2 mmol) and cesium carbonate (16.3 mg,0.05 mmol) and 1b (80 mg,0.4 mmol) into a 4ml reaction bottle, adding a pre-complexed copper catalyst into the reaction bottle, reacting the mixture for 2 hours at room temperature, spinning the reaction solution, separating the mixture by silica gel column chromatography to obtain a target product 3c, eluting with ethyl acetate and petroleum ether (volume ratio is 0.1:1), and obtaining 96% of yield.
Characterization data for the resulting product 3c are as follows:
white solid (90 mg,91% ee)
1 H NMR(400MHz,CDCl 3 )δ:7.59-7.02(m,4H),6.46(s,1H),5.02(s,1H),4.05(m,2H),3.50(dt,J＝8.8,3.6Hz,1H),3.46(t,J＝8.8Hz,1H),2.88(br,1H),1.52(s,9H),1.18(t,J＝7.2Hz,3H)ppm.
13 C NMR(100MHz,CDCl 3 )δ:175.6,171.6,150.8,140.2,133.4,129.5,128.0,127.6,123.4,98.5,84.4,64.1,62.9,61.8,49.3,48.7,27.6,14.0ppm.
Example 4
Copper triflate and (S) -DTBM-SEGPHOS in dichloromethane are stirred at room temperature for thirty minutes under nitrogen atmosphere, 4a (44.2 mg,0.2 mmol) and cesium carbonate (16.3 mg,0.05 mmol) and 1b (80 mg,0.4 mmol) are sequentially added into a 4ml reaction bottle, a pre-complexed copper catalyst is added into the reaction bottle, the mixture is reacted for 2 hours at room temperature, the reaction solution is dried in a spinning manner, the target product 4c is obtained through silica gel column chromatography separation, the eluent is ethyl acetate and petroleum ether (volume ratio is 0.05:1), and the yield is 78%.
Characterization data for the resulting product 4c are as follows:
white solid (66.7 mg,93% ee)
1 H NMR(400MHz,CDCl 3 )δ:7.34-7.30(m,2H),6.69-6.67(m,2H),6.47(s,1H),4.50(d,J＝2.8Hz,1H),4.30-4.00(m,2H),3.79(s,3H),3.38-3.30(m,2H),2.59(br,1H),1.51(s,9H),1.25(t,J＝7.2Hz,3H)ppm.
13 C NMR(100MHz,CDCl 3 )δ:176.1,170.8,159.4,150.9,133.1,127.7,114.1,98.2,84.4,64.8,63.1,55.3,50.1,27.6,14.0ppm
Example 5
Under nitrogen atmosphere, stirring a dichloromethane solution of copper triflate and (S) -DTBM-SEGPHOS for thirty minutes at room temperature, sequentially adding 5a (39.4 mg,0.2 mmol) and cesium carbonate (16.3 mg,0.05 mmol) and 1b (80 mg,0.4 mmol) into a 4ml reaction bottle, adding a pre-complexed copper catalyst into the reaction bottle, reacting the mixture for 6 hours at zero ℃, spinning the reaction solution, separating the mixture by a silica gel column chromatography to obtain a target product 5c, wherein the eluent is ethyl acetate and petroleum ether (volume ratio is 0.1:1), and the yield is 75%.
Characterization data for the resulting product 5c are as follows:
white solid (60 mg,91% ee)
1 H NMR(400MHz,CDCl 3 )δ:7.25-7.23,7.10-6.90(m,3H),6.46(s,1H),4.90(s,1H),4.13(qq,J＝10.4,7.2Hz,2H),3.84(s,1H),3.50(s,1H),3.50(s,1H),2.70(br,1H),1.52(s,9H),1.22(t,J＝7.2Hz,3H)ppm.
13 C NMR(100MHz,CDCl 3 )δ:175.5,170.9,150.8,145.1,127.1,125.3,124.7,98.7,84.5,63.1,62.0,60.9,51.1,27.6,14.0ppm.
Example 6
Under nitrogen atmosphere, stirring a dichloromethane solution of copper triflate and (S) -DTBM-SEGPHOS for thirty minutes at room temperature, sequentially adding 5a (39.4 mg,0.2 mmol) and cesium carbonate (16.3 mg,0.05 mmol) and 1b (80 mg,0.4 mmol) into a 4ml reaction bottle, adding a pre-complexed copper catalyst into the reaction bottle, reacting the mixture at room temperature for 6 hours, spinning the reaction solution, separating the mixture by silica gel column chromatography to obtain a target product 5c, eluting with ethyl acetate and petroleum ether (volume ratio is 0.1:1), and obtaining the yield of 75%.
Characterization data for the resulting product 5c are as follows:
white solid (60 mg,90% ee)
1 H NMR(400MHz,CDCl 3 )δ:7.25-7.23,7.10-6.90(m,3H),6.46(s,1H),4.90(s,1H),4.13(qq,J＝10.4,7.2Hz,2H),3.84(s,1H),3.50(s,1H),3.50(s,1H),2.70(br,1H),1.52(s,9H),1.22(t,J＝7.2Hz,3H)ppm.
13 C NMR(100MHz,CDCl 3 )δ:175.5,170.9,150.8,145.1,127.1,125.3,124.7,98.7,84.5,63.1,62.0,60.9,51.1,27.6,14.0ppm.
Example 7
Under nitrogen atmosphere, stirring a dichloromethane solution of copper triflate and (S) -DTBM-SEGPHOS for thirty minutes at room temperature, sequentially adding 7a (56.2 mg,0.2 mmol) and cesium carbonate (16.3 mg,0.05 mmol) and 1b (80 mg,0.4 mmol) into a 4ml reaction bottle, adding a pre-complexed copper catalyst into the reaction bottle, reacting the mixture for 3 hours at room temperature, spinning the reaction solution, separating the mixture by silica gel column chromatography to obtain a target product 7c, eluting with ethyl acetate and petroleum ether (volume ratio is 0.1:1), and obtaining the yield of 57%.
Characterization data for the resulting product 7c are as follows:
white solid (44 mg,93% ee)
1 H NMR(400MHz,CDCl 3 )δ:7.35(m,7H),7.20(dd,J＝14.4,7.2Hz,3H),6.51(s,1H),4.56(s,1H),4.19(m,2H),3.79(s,1H),3.32(m,2H),2.68(t,J＝7.6Hz,2H),2.59(s,1H),2.04-1.91(m,2H),1.48(s,9H),1.28(d,J＝10.8Hz,3H)ppm.
13 C NMR(100MHz,CDCl 3 )δ:176.21,170.93,150.93,141.36,140.78,128.84,128.49,128.02,126.41,126.29,98.20,84.44,77.42,77.10,76.78,65.14,32.15,31.51,30.23,30.02,29.72,27.60ppm.
Example 8
Under nitrogen atmosphere, stirring a dichloromethane solution of copper triflate and (S) -DTBM-SEGPHOS for thirty minutes at room temperature, sequentially adding 1a (95.5 mg,0.5 mmol) and cesium carbonate (40.6 mg,0.125 mmol) and 2b (142 mg,1.0 mmol) into a 20ml reaction bottle, adding a pre-complexed copper catalyst into the reaction bottle, reacting the mixture for 3 hours at room temperature, spinning the reaction solution, separating the mixture by silica gel column chromatography to obtain a target product 8c, eluting with ethyl acetate and petroleum ether (volume ratio is 0.1:1), and obtaining the yield of 74%.
Characterization data for the resulting product 8c are as follows:
white solid (122 mg,97% ee)
1 H NMR(400MHz,CDCl 3 )δ:7.36(m,5H),6.64(s,1H),4.60(d,J＝4.0Hz,1H),4.16(m,2H),3.85(d,J＝8.4Hz,1H),3.40(dd,J＝8.8,4.0Hz,1H),3.31(t,J＝8.4Hz,1H),2.12(s,3H),1.25(t,J＝7.2Hz,3H)ppm.
13 C NMR(100MHz,CDCl 3 )δ:176.28,170.96,168.70,141.38,128.77,127.94,126.42,95.96,65.00,63.19,61.80,50.97,50.06,20.78,14.06ppm.
Example 9
Under nitrogen atmosphere, a dichloromethane solution of copper triflate and (S) -DTBM-SEGPHOS is stirred for thirty minutes at room temperature, 9a (94.5 mg,0.2 mmol) and cesium carbonate (16.3 mg,0.05 mmol) and 1b (80 mg,0.4 mmol) are sequentially added into a 20ml reaction bottle, a pre-complexed copper catalyst is added into the reaction bottle, the mixture is reacted for 3 hours at room temperature, the reaction solution is dried in a spinning manner, the target product 9c is obtained through silica gel column chromatography separation, the eluent is ethyl acetate and petroleum ether (volume ratio is 0.1:1), and the yield is 83%.
Characterization data for the resulting product 9c are as follows:
white solid (112 mg, > 20:1dr)
1 H NMR(400MHz,CDCl 3 )δ:8.01(d,J＝7.6Hz,2H),7.56(d,J＝1.6Hz,2H),6.50(s,1H,),5.94(d,J＝3.6Hz,1H),5.49(d,J＝2Hz,1H),4.63(s,1H),4.62(s,1H),4.42-4.28(m,2H),4.23(m,1H 3 ),4.23(m,1H),4.16-4.03(m,2H),3.87(s,1H),3.33(m,1H),3.33(m,1H),3.1-2.3(br,1H),1.55(s,3H),1.41(s,3H),1.32(s,3H),1.30(t,J＝7.2Hz,3H),1.20(s,3H)ppm.
13 C NMR(100MHz,CDCl 3 )δ:183.9,182.2,170.7,169.7,130.2,126.7,112.4,112.0,109.4,109.1,105.5,94.6,85.3,84.6,83.4,80.0,72.6,67.3,65.7,64.1,62.0,46.5,43.1,27.6,26.9,26.7,26.2,25.2(OCCH 3 ),14.1(COOCH 2 CH 3 )ppm.
The above embodiments of the present invention are only some embodiments of the present invention, and the present invention is not limited in any way, and any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention falls within the technical scope of the present invention.

Claims (11)

1. A method for synthesizing chiral pyrrole bridged ring compounds comprises the following steps:
in an organic solvent, catalyzing by a copper catalysis system or a silver catalysis system, and carrying out asymmetric [3+2] cycloaddition reaction on an imido ester compound I and a butenolide compound II in the presence of cesium carbonate to obtain a chiral pyrrole bridged ring compound III; the copper catalytic system consists of copper salt and chiral ligand IV, wherein the chiral ligand has a structure shown in a formula IV; the silver catalytic system consists of silver salt and chiral ligand V, and the chiral ligand has a structure shown in a formula V;
wherein in the compound I, R 1 Is phenyl, halogenated phenyl and C 1 ～C 8 Alkyl-substituted phenyl, diacetone glucose ester-substituted phenyl, C 1 ～C 8 Alkoxy-substituted phenyl, trifluoromethyl-substituted phenyl, boric acid-substituted phenyl, cyano-substituted phenyl, azaalkyl-substituted phenyl, biphenyl, naphthyl, thienyl, halofuryl, C 1 ～C 8 An alkyl group; r is R 2 Is C 1 ～C 8 Alkyl, C 1 ～C 8 Alkenyl-substituted C 1 ～C 8 Alkyl, silyl; r is R 3 Is hydrogen radical, C 1 ～C 8 An alkyl group;
in the compound II, R 4 Is C 1 ～C 8 Alkyl, C 1 ～C 8 Alkoxy, alkylacyloxy, (hetero) arylacyloxy;
in the compound III, the substituent R 1 、R 2 、R 3 Respectively with R in the compound I 1 、R 2 、R 3 The same; substituent R 4 With R in compound II 4 The same applies.
2. According to claim 1A method for synthesizing chiral pyrrole bridged ring compounds is characterized in that in the compound I, R 1 4-methoxyphenyl, 4-trifluoromethylphenyl, 3-chlorophenyl, 2-bromophenyl, 4-fluorophenyl, 4-iodophenyl, 4-pinacol-ester-phenyl-borate, 4- (N, N-dimethyl) phenyl, 4-biphenyl, 2-naphthyl, 3-cyanophenyl, 2-thienyl; r is R 2 Is tert-butyl, trimethylsilylethyl, phenethyl, phenylpropyl; r is R 3 Is a hydrogen atom, methyl; in the compound II, R4 is acetoxy or benzoyloxy; in the compound III, the substituent R 1 、R 2 、R 3 Respectively with R in the compound I 1 、R 2 、R 3 The same; substituent R 4 With R in compound II 4 The same applies.
3. The method for synthesizing chiral pyrrole bridged ring compounds according to claim 1, wherein the solvent is dichloromethane or toluene; the ratio of the volume of the solvent to the mole number of the imido ester compound I is 1mL:0.1mmol; the solvent is anhydrous.
4. The method for synthesizing chiral pyrrole bridged ring compounds according to claim 1, wherein the copper catalyst is copper triflate; the molar ratio of the copper catalyst to the imido ester compound I is 0.02:0.1; the molar ratio of copper in the copper catalyst to chiral ligand IV is 1:1.
5. the method for synthesizing chiral pyrrole bridged ring compounds according to claim 1, wherein the silver catalyst is silver acetate; the mol ratio of the silver catalyst to the imido ester compound I is 0.02:0.1; the molar ratio of silver to chiral ligand V in the silver catalyst is 1:1.
6. the method for synthesizing chiral pyrrole bridged ring compounds according to claim 1, wherein the molar ratio of cesium carbonate to imidoester compound I is 1:4, a step of; the molar ratio of the compound of formula I to the compound of formula II is 1:2.
7. the method for synthesizing chiral pyrrole bridged ring compounds according to claim 1, wherein the copper catalyst is prepared by the following method: copper salt and chiral ligand IV are added into methylene dichloride under the protection of nitrogen, and stirred for 30 minutes at room temperature, and the obtained solution is a copper catalyst system.
8. The method for synthesizing chiral pyrrole bridged ring compounds according to claim 1, wherein the silver catalyst is prepared according to the following method: under the protection of nitrogen, silver salt and chiral ligand V are added into toluene, and stirred for 30 minutes at room temperature, and the obtained solution is a silver catalyst system.
9. The method for synthesizing chiral pyrrole bridged ring compounds according to claim 1, wherein the cycloaddition reaction is performed under an inert gas atmosphere, and the inert gas is nitrogen.
10. The method for synthesizing chiral pyrrole bridged ring compounds according to claim 1, wherein the cycloaddition reaction temperature is 0 ℃ to 25 ℃; the cycloaddition reaction time is 2-7 hours.
11. The method for synthesizing chiral pyrrole bridged ring compounds according to claim 1, wherein after the [3+2] cycloaddition reaction of the imidoester compound I and the butenolide compound II, the product separation and characterization can be performed by a conventional separation and purification method. The specific post-reaction treatment steps are as follows: removing the solvent from the reaction solution, separating the obtained crude product by silica gel column chromatography to obtain chiral pyrrole bridged ring compound III, wherein the eluent is a mixed solvent of ethyl acetate and petroleum ether, and the volume ratio of the mixed solvent of ethyl acetate and petroleum ether in the mixed solvent is 0.05-0.2: 1.
CN202311327144.3A 2023-10-13 2023-10-13 Synthesis method of chiral pyrrole bridged ring compound Pending CN117384177A (en)

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