CN115286605B - Method for synthesizing isochromanone compounds based on carbon monoxide gas or carbon monoxide alternative source - Google Patents

Method for synthesizing isochromanone compounds based on carbon monoxide gas or carbon monoxide alternative source Download PDF

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CN115286605B
CN115286605B CN202210998117.8A CN202210998117A CN115286605B CN 115286605 B CN115286605 B CN 115286605B CN 202210998117 A CN202210998117 A CN 202210998117A CN 115286605 B CN115286605 B CN 115286605B
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CN115286605A (en
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周强辉
程鸿刚
刘畅
张欣萍
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Wuhan University WHU
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/76—Benzo[c]pyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

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Abstract

The invention discloses a method for synthesizing isochromanone compounds based on carbon monoxide gas or carbon monoxide substitution source. The method takes simple and easily obtained aryl iodide, epoxide and carbon monoxide molecules as initial raw materials, and under the action of a palladium catalyst, phosphine ligand, norbornene derivatives and alkali, the raw materials are stirred and reacted in an organic solvent at 40-100 ℃ to obtain the isochromanone compound. The method has the advantages of low cost and easy acquisition of raw materials, mild reaction conditions, simple preparation process, good chemical selectivity, wide substrate application range, easy amplification and the like, has great application potential, and lays a good foundation for industrial production.

Description

Method for synthesizing isochromanone compounds based on carbon monoxide gas or carbon monoxide alternative source
Technical Field
The invention belongs to the field of organic synthesis, and relates to a method for synthesizing an isochromanone compound based on carbon monoxide gas or a carbon monoxide alternative source.
Background
Isochromanone is an important class of heterocyclic compounds and pharmacophores, which are widely found in many bioactive molecules. Molecules containing such backbones generally have a variety of pharmacological properties, such as antibacterial, anti-inflammatory, anti-ulcer and anti-tumor properties (1J. Med. Chem.1981,24,194; 2 Bi. Chem. Pharmacol.2002,63,421; 3J. Nat. Prod.2003,66,709; 4J. Nat. Prod.2004,67, 1604.). The synthesis method of the compound is continuously developed and enriched, and the synthesis strategies are mainly divided into four types according to the substrate structure: (1) Oxidation of isochroman compounds ([ 5] org. Lett.1999,1,2129; [6] J. Am. Chem. S. Deg.C. 2002,124,4198; [7] adv. Synth. Catalyst.2011, 353,401; [8] org. Lett.2015,17, 5492.); (2) Cycloaddition of carbonyl compounds ([ 9] Angew.chem.int.ed.2008,47,5820; [10] org.Lett.2016,18,4444; [11] org.Lett.2018,20,333; [12] Angew.chem.int.ed.2020,59, 3190.); (3) Carbonylation cyclization of phenethyl alcohol derivatives ([ 13] chem. Sci.2011,2,967; [14] chem. Eu. J.2016,22,6234; [15] Synthesis.2018,50, 3015.); (4) Cyclization of benzoic acid derivatives ([ 16] Angew.chem.int.ed.2009,48,6097; [17] J.am.chem.S. Pat. No. 2015,137,10950; [18] adv.synth.catalyst.2019, 361, 983.).
Although the preparation methods are mature and effective, certain limitations exist, such as harsh reaction conditions, resulting in limited compatibility of functional groups; the reaction substrate is special and needs longer synthesis steps to prepare; the structure of the prepared isochromanone product lacks diversity. Therefore, the further development reaction condition is mild, the raw materials are simple and easy to obtain, and the novel synthesis strategy with good substrate compatibility has important value and research significance.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a method for synthesizing the isochromanone compound based on carbon monoxide gas or carbon monoxide alternative sources. The method has the advantages of cheap and easily obtained raw materials, mild reaction conditions, simple preparation process, good chemical selectivity and wide substrate application range.
The technical scheme provided by the invention is as follows:
a method for synthesizing isochromanone based on carbon monoxide gas or a carbon monoxide alternative source, comprising the steps of:
under the atmosphere of protective gas, aryl iodide A, epoxy compound B and carbon monoxide gas C or carbon monoxide substitution source K are taken as initial raw materials, under the action of palladium catalyst D, phosphine ligand E, norbornene derivative F and alkali G, additive H is added, stirring reaction is carried out in organic solvent I until the reaction is completed, and after the reaction is completed, the reactants are separated to obtain the heterochromatic ketone compound shown in formula J; wherein when carbon monoxide is the starting material, carbon monoxide is dissolved in solvent M and base L is added to produce carbon monoxide;
the reaction equation is as follows:
wherein R is 1 Is one or more of alkyl, aryl, ester, amido, alkoxy, benzyloxy, tert-butyloxycarbonyl and halogen; r is R 2 Is one or more of alkyl, aryl, ester group, hydroxyl, amide group, alkoxy, halogenated alkyl, phenoxy, benzyloxy, oxycarbazole, phthalic acid amide, natural product derivatives such as gibberellin and estrone. x represents R 1 X is more than or equal to 0 and less than or equal to 3, R 1 The substitution position on the aromatic ring is defined by the 2-5 position; y represents R 2 Y=1.
Further, R 1 And R is 2 In the substituents of (a): the alkyl group is an alkyl group having 1 to 16 carbon atoms such as methyl, ethyl, isopropyl, decyl, hexadecyl, etc.; aryl is phenyl, condensed ring aromatic ring and substituted aromatic hydrocarbon, and the substituent comprises C1-C6 alkyl, C1-C6 alkoxy, halogen and the like; the ester group is-COOR, wherein R is an alkyl group having 1 to 3 carbon atoms, including methyl group and the like; alkoxy means an alkoxy group having 1 to 10 carbon atoms, such as methoxy and the like; halogen means fluorine, chlorine, bromine, iodine; haloalkyl is C1-C6 haloalkyl, e.g. -CH 2 Cl。
Further, the carbon monoxide gas C is a mixed gas of carbon monoxide and inert gas, and the mixing volume ratio is any one of 1:1 to 1:20. The preferred mixture ratio is carbon monoxide: argon = 1:7.
further, the palladium catalyst D is Pd (PPh 3 ) 4 、Pd(dba) 2 、Pd 2 (dba) 3 、Pd(OAc) 2 、Pd(PhCN) 2 Cl 2 、Pd(MeCN) 2 Cl 2 、PdCl 2 、PdI 2 、[Pd(allyl)Cl] 2 Any one or more of the following. The preferred palladium catalyst D is Pd (OAc) 2 。
Further, the phosphine ligand E is any one or more of 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl, 2-di-tert-butylphosphino-2 ',4',6' -triisopropylbiphenyl, 2-dicyclohexylphosphine-2 ' - (N, N-dimethylamino) biphenyl, 2-di-tert-butylphosphine-2- (N, N-dimethylamino) biphenyl, triarylphosphine, tri (2-furyl) phosphine and bis (2-diphenylphosphinophenyl) ether. The preferred phosphine ligand E is 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl.
Further, the norbornene derivative F has a structural formula:
wherein:
i)R 3 p represents the number of substituents, and p is more than or equal to 0 and less than or equal to 8; r is R 4 Q represents the number of substituents, and q is more than or equal to 0 and less than or equal to 2;
ii) the number of substituents on the left five-membered ring is 2 or more, and may be the same or different; when the number of substituents on the double bond is 2, the substituents may be the same or different;
iii)R 3 and R is 4 The types of the substituents may be the same or different;
iii) Each R 3 And R is 4 Independently an ester group, a carboxyl group, a cyano group, an amide group, an alkoxy group, an aryl group, a heterocyclic aryl group, an alkyl group.
Further, the ester group in the norbornene derivative F is-COOR, wherein R is alkyl with 1-2 carbon atoms, including methyl and ethyl; alkoxy is an alkoxy group having 1 to 10 carbon atoms; aryl is phenyl, condensed ring aromatic ring and substituted aromatic hydrocarbon, and the substituent comprises C 1-6 Alkyl, C 1-6 Alkoxy, halogenEtc.; the heterocyclic aryl is a quinoline group; the alkyl group has 1 to 6 carbon atoms and includes methyl, ethyl, isopropyl, hexyl and the like. 2-norbornene-5, 6-ethanediamide quinoline, 2-norbornene-5-carboxanilide or 2-norbornene-5, 6-ethanediamide biphenyl is preferred as cocatalyst.
Further, the alkali G is any one or more of potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, tripotassium phosphate and potassium tert-butoxide. Preferably, the base G is potassium acetate.
Further, the additive H is any one or more of methanol, ethanol, isopropanol, tertiary butanol, trifluoroethanol, hexafluoroisopropanol, formic acid, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, phenol, m-chlorophenol, p-trifluoromethylphenol, p-nitrophenol, hydrochloric acid, hydrobromic acid and hydroiodic acid. Preferably, additive H is ethanol.
Further, the solvent I is methanol, ethanol, isopropanol, tertiary butanol, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, dimethylethylene glycol, methyl tertiary butyl ether, 1, 4-dioxane, 1, 3-dioxane, dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, C 4-12 Saturated alkane, C 3-12 Fluorinated or chlorinated alkanes, benzene, toluene, xylene, trimethylbenzene, dimethylsulfoxide, N-dimethylformamide, N-dimethylacetamide, acetone, N-methylpyrrolidone, acetonitrile, C 3-12 Any one or more of the saturated alkyl nitriles. Preferably, the solvent I is N-methylpyrrolidone.
Further, the alkali L is any one or more of sodium bicarbonate, sodium acetate, cesium carbonate, potassium phosphate, triethylamine, triethylene diamine, pyridine and 4-dimethylaminopyridine. Preferably, the base L is triethylamine.
Further, the solvent M is methanol, ethanol, isopropanol, tertiary butanol, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, dimethylethylene glycol, methyl tertiary butyl ether, 1, 4-dioxane, 1, 3-dioxane, dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, C 4-12 Saturated alkane, C 3-12 Fluorinated or chlorinated alkanes, benzene, methylBenzene, xylene, trimethylbenzene, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, acetone, N-methylpyrrolidone, acetonitrile, C 3-12 Any one or more of the saturated alkyl nitriles. Preferably, the solvent M is 1, 4-dioxane.
Further, the feeding mole ratio of each raw material is as follows:
in the first condition, aryl iodide A, epoxy compound B, catalyst D, phosphine ligand E, norbornene derivative F, alkali G=1.0:3.0:0.05-0.1:0.1-0.2:0.5:1.0. The ratio of the above raw materials is preferably 1.0:3.0:0.1:0.2:0.5:1.0.
In condition II, aryl iodide A, epoxy compound B, para-trifluoromethyl formate aryl ester C: catalyst D phosphine ligand E norbornene derivative F alkali G=1.0:3.0:1.2:0.05-0.1:0.12-0.24:0.2-0.5:1.5. Preferably, the ratio of the raw materials is 1.0:3.0:1.2:0.05:0.12:0.2:1.5 or 1.0:3.0:1.2:0.1:0.24:0.5:1.5.
Further, the shielding gas is selected from argon or nitrogen. Argon is preferred.
Further, the reaction temperature is 40-100 ℃. The reaction temperature is preferably 60 ℃.
Further, the reaction time is 16-24 hours. The reaction time is preferably 16h.
Further, the reactant is isolated by extracting, concentrating and purifying the reaction mixture by column chromatography. The extraction mode uses ethyl acetate and saturated sodium chloride solution. The concentration may be carried out by distillation under reduced pressure, for example, by rotary evaporation. The purification method can adopt column chromatography separation and purification.
Compared with the prior art, the method provided by the invention has the following beneficial effects that a series of isochromanone compounds can be synthesized:
i) The main raw materials of aryl iodide and epoxy compound are commercial reagents, the price is low, the variety is various, and the construction of the isochromanone skeleton is completed in one step by multiple components;
ii) the method can realize the efficient construction of the isochromanone compounds by using carbon monoxide gas or simple and easy-to-prepare para-trifluoromethyl aryl formate as a carbonyl source;
iii) The method has good substrate application range and functional group compatibility.
Detailed Description
The present invention will be further described with reference to the following specific examples, to which the present invention is not limited.
Example 1: preparation of Compound J-1
Palladium acetate (2.3 mg,0.01 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (11.5 mg,0.12 mmol), potassium acetate (29.4 mg,0.3 mmol) and 2-norbornene-5-carboxamide (8.6 mg,0.04 mmol) were added to the carbon monoxide-depleted chamber of the dried and magnetically stirred double chamber reactor tube, respectively, in a glove box. 2-methyl iodobenzene (43.6 mg,0.2 mmol), benzyl glycidyl ether (98.5 mg,0.6 mmol) and dried N-methyl pyrrolidone (1.0 mL) were then added; to the carbon monoxide formation chamber were added phenyl 4-trifluoromethylcarboxylate (45.6 mg,0.24 mmol), triethylamine (24.3 mg,0.24 mmol) and dried 1, 4-dioxane (1.0 mL), respectively. The reaction was carried out at 60℃for 16 hours under an argon atmosphere. The mixture in the carbon monoxide-consuming chamber was extracted with ethyl acetate and saturated sodium chloride solution, dried over anhydrous sodium sulfate, the solvent was removed by distillation under reduced pressure, and the compound J-1 was isolated and purified by column chromatography (pale yellow oily substance, 78% yield). 1 H NMR(400MHz,CDCl 3 ):δ7.42–7.27(m,6H),7.19(d,J＝7.7Hz,1H),7.08(d,J＝7.5Hz,1H),4.65–4.57(m,3H),3.79(dd,J＝10.3,4.9Hz,1H),3.72(dd,J＝10.3,5.3Hz,1H),3.11(dd,J＝16.1,11.6Hz,1H),2.94(dd,J＝16.1,3.1Hz,1H),2.67(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ164.5,143.1,140.0,137.9,132.9,131.2,128.6,128.0,127.9,125.5,123.8,76.7,73.8,71.2,31.6,22.4；HRMS(ESI-TOF):calc’d for C 18 H 18 NaO 3 [M+Na+]305.1148,found 305.1150.
Example 2: preparation of Compound J-2
The procedure was as in example 1 except that the epoxy compound used was S-benzyl glycidyl ether (98.5 mg,0.6 mmol) to give compound J-2 (pale yellow oil, 78% yield, 99% ee). 1H NMR (400 MHz, CDCl) 3 )δ7.42–7.27(m,6H),7.19(d,J＝7.7Hz,1H),7.08(d,J＝7.5Hz,1H),4.68–4.56(m,3H),3.79(dd,J＝10.2,4.8Hz,1H),3.72(dd,J＝10.3,5.3Hz,1H),3.11(dd,J＝16.1,11.6Hz,1H),2.94(dd,J＝16.1,3.0Hz,1H),2.67(s,3H)；13C NMR(100MHz, CDCl3 )δ164.5,143.1,140.0,137.9,132.9,131.2,128.6,128.0,127.9,125.5,123.8,76.7,73.8,71.2,31.5,22.3；HRMS(ESI-TOF):calc’d for C18H18NaO3[M+Na+]305.1148,found 305.1150；HPLC:Daicel Chiralpak IG column,10％iPrOH in nhexane,1mL/min,λ＝230nm,tR(major)＝18.524min,tR(minor)＝19.927min；[α]23D:-93.684(c＝0.57,CHCl 3 ).
Example 3: preparation of Compound J-3
The procedure was as in example 1 except that 2-ethyliodobenzene (46.4 mg) was used as the iodide to give compound J-3 (pale yellow oil, 70% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.40(t,J＝7.6Hz,1H),7.37–7.27(m,5H),7.23(d,J＝7.7Hz,1H),7.08(d,J＝7.5Hz,1H),4.64–4.56(m,3H),3.78(dd,J＝10.3,4.9Hz,1H),3.71(dd,J＝10.3,5.3Hz,1H),3.16–3.05(m,3H),2.94(dd,J＝16.1,3.0Hz,1H),1.25(t,J＝7.5Hz,3H)；13C NMR(100MHz,CDCl 3 )δ164.1,149.2,140.1,137.9,133.1,129.8,128.6,128.0,127.9,125.5,123.2,76.6,73.8,71.2,31.7,27.8,15.7；HRMS(ESI-TOF):calc’d for C 19 H 20 NaO 3 [M+Na+]319.1304,found 319.1306.
Example 4: preparation of Compound J-4
The procedure was as in example 1 except that 2-isopropyl iodobenzene (49.2 mg) was used as the iodide to give compound J-4 (pale yellow oil, 62% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.47–7.38(m,2H),7.38–7.27(m,5H),7.06(d,J＝7.2Hz,1H),4.66–4.55(m,3H),4.15(hept,J＝6.9Hz,1H),3.79(dd,J＝10.2,5.0Hz,1H),3.71(dd,J＝10.3,5.3Hz,1H),3.09(dd,J＝16.0,11.6Hz,1H),2.93(dd,J＝16.0,2.9Hz,1H),1.30(d,J＝6.8Hz,3H),1.21(d,J＝6.9Hz,3H)；13C NMR(100MHz,CDCl 3 )δ164.08,153.73,139.76,137.90,133.04,128.64,128.01,127.92,126.03,125.10,123.11,76.57,73.80,71.21,32.07,29.08,24.22,24.00；HRMS(ESI-TOF):calc’d for C 20 H 22 NaO 3 [M+Na+]333.1463,found 333.1461.
Example 5: preparation of Compound J-5
The procedure was as in example 1 except that 2-ethoxyiodobenzene (49.6 mg), palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol) and (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) were used as iodides to give compound J-5 (colorless oily liquid, 53% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.41(t,J＝8.0Hz,1H),7.37–7.27(m,5H),6.89(d,J＝8.5Hz,1H),6.78(d,J＝7.5Hz,1H),4.63–4.54(m,3H),4.24–4.08(m,2H),3.78(dd,J＝10.2,4.8Hz,1H),3.70(dd,J＝10.2,5.6Hz,1H),3.05(dd,J＝16.1,11.4Hz,1H),2.92(dd,J＝16.1,3.0Hz,1H),1.49(t,J＝7.0Hz,3H)；13C NMR(100MHz,CDCl 3 )δ162.0,160.7,141.7,137.9,134.5,128.6,128.0,127.9,119.3,114.1,112.2,76.4,73.8,71.2,64.9,31.7,14.8；HRMS(ESI-TOF):calc’d for C 19 H 20 NaO 4 [M+Na+]335.1253,found 335.1251.
Example 6: preparation of Compound J-6
The procedure was as in example 1 except that 2-benzyloxyiodobenzene (62.0 mg), palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol) and (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) were used as iodides to give compound J-6 (colorless oily liquid, 51% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.54(d,J＝7.4Hz,2H),7.43–7.33(m,7H),7.30(dd,J＝8.0,3.9Hz,2H),6.93(d,J＝8.5Hz,1H),6.82(d,J＝7.5Hz,1H),5.31–5.19(m,2H),4.65–4.56(m,3H),3.79(dd,J＝10.3,4.8Hz,1H),3.72(dd,J＝10.3,5.5Hz,1H),3.09(dd,J＝16.2,11.4Hz,1H),2.94(dd,J＝16.1,3.0Hz,1H)；13C NMR(100MHz,CDCl 3 )δ161.9,160.2,141.8,137.9,136.7,134.5,128.7,128.6,128.0,127.9,127.9,126.8,119.9,114.5,113.0,76.5,73.8,71.2,70.7,31.6；HRMS(ESI-TOF):calc’d for C 24 H 22 NaO 4 [M+Na+]397.1410,found 397.1401.
Example 7: preparation of Compound J-7
The procedure was as in example 1 except that methyl o-iodophenylacetate (55.2 mg), palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol) and (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) were used as iodides to give compound J-7 (pale yellow oily liquid, 53% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.46(t,J＝7.6Hz,1H),7.39–7.27(m,5H),7.20(dd,J＝7.7,3.5Hz,2H),4.67(dtd,J＝11.5,5.0,3.1Hz,1H),4.62(d,J＝1.3Hz,2H),4.22(d,J＝16.8Hz,1H),3.95(d,J＝16.9Hz,1H),3.77(d,J＝4.7Hz,1H),3.75–3.71(m,1H),3.70(s,3H),3.16(dd,J＝16.2,11.5Hz,1H),2.98(dd,J＝16.2,3.1Hz,1H)；13C NMR(100MHz,CDCl 3 )δ172.0,164.5,140.3,138.2,137.9,133.2,131.7,128.6,128.0,127.9,127.3,124.2,76.8,73.8,71.1,52.1,40.6,31.3；HRMS(ESI-TOF):calc’d for C 20 H 20 NaO 5 [M+Na+]363.1202,found 363.1200.
Example 8: preparation of Compound J-8
The procedure was as in example 1 except that the iodide used was ortho-tert-butyldimethyl-protected methylol iodobenzene (69.6 mg), palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol), (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) to give compound J-8 (colorless oily liquid, 63% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.82(d,J＝7.9Hz,1H),7.54(t,J＝7.7Hz,1H),7.39–7.28(m,5H),7.14(d,J＝7.5Hz,1H),5.27(d,J＝16.9Hz,1H),5.08(d,J＝16.9Hz,1H),4.67–4.58(m,3H),3.78(dd,J＝10.3,4.8Hz,1H),3.72(dd,J＝10.3,5.2Hz,1H),3.13(dd,J＝16.2,11.5Hz,1H),2.97(dd,J＝16.2,3.2Hz,1H),0.98(s,9H),0.14(d,J＝6.1Hz,6H)；13C NMR(100MHz,CDCl 3 )δ164.2,146.9,139.5,137.8,133.4,128.6,128.0,127.9,125.9,125.6,121.3,76.9,73.8,71.1,63.4,31.2,26.2,18.6,-5.2；HRMS(ESI-TOF):calc’d for C 24 H 32 SiNaO 4 [M+Na+]435.1964,found 435.1962.
Example 9: preparation of Compound J-9
The procedure was as in example 1 except that 2-methyl-3-fluoroiodobenzene (47.2 mg) was used as the iodide to give compound J-9 (yellow oily liquid, 77% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.39–7.28(m,5H),7.17(t,J＝8.8Hz,1H),7.05(dd,J＝8.4,5.1Hz,1H),4.64–4.56(m,3H),3.78(dd,J＝10.3,4.8Hz,1H),3.71(dd,J＝10.3,5.3Hz,1H),3.11–3.02(m,1H),2.92(dd,J＝16.1,3.1Hz,1H),2.57(d,J＝2.4Hz,3H)；13C NMR(100MHz,CDCl 3 )δ163.8(d,J＝3.0Hz),162.0,159.6,137.8,135.5,129.8(d,J＝17.6Hz),128.3(d,J＝73.3Hz),128.1,126.0(d,J＝8.1Hz),125.5(d,J＝4.3Hz),119.9(d,J＝24.2Hz),77.0,73.8,71.1,31.1,12.4(d,J＝6.4Hz)；19F NMR(377MHz,CDCl 3 )；δ-116.2；HRMS(ESI-TOF):calc’d for C 18 H 17 FNaO 3 [M+Na+]323.1053,found 323.1045.
Example 10: preparation of Compound J-10
The procedure was as in example 1 except that 2-methyl-3-chloroiodobenzene (50.4 mg) was used as the iodide to give compound J-10 (yellow oily liquid, 72% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.49(d,J＝8.1Hz,1H),7.39–7.28(m,5H),7.03(d,J＝8.1Hz,1H),4.64–4.55(m,3H),3.78(dd,J＝10.3,4.8Hz,1H),3.71(dd,J＝10.3,5.3Hz,1H),3.07(dd,J＝16.2,11.5Hz,1H),2.92(dd,J＝16.2,3.0Hz,1H),2.72(s,3H)；13C NMR(100MHz,CDCl 3 )δ163.7,140.5,138.6,137.8,135.5,133.7,128.7,128.1,127.9,126.0,125.9,76.8,73.9,71.0,31.5,18.1；HRMS(ESI-TOF):calc’d for C 18 H 17 ClNaO 3 [M+Na+]339.0758,found 339.0759.
Example 11: preparation of Compound J-11
The procedure was as in example 1 except that 2, 3-dimethyliodobenzene (46.4 mg) was used as the iodide to give compound J-11 (pale yellow oily liquid, 78% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.36(d,J＝4.3Hz,4H),7.32–7.26(m,2H),6.97(d,J＝7.7Hz,1H),4.62(s,2H),4.57(dtd,J＝11.5,5.1,2.9Hz,1H),3.78(dd,J＝10.2,5.0Hz,1H),3.70(dd,J＝10.3,5.3Hz,1H),3.05(dd,J＝16.0,11.6Hz,1H),2.89(dd,J＝16.0,3.0Hz,1H),2.58(s,3H),2.32(s,3H)；13C NMR(100MHz,CDCl 3 )δ164.9,141.2,137.9,137.5,137.5,134.4,128.6,128.0,127.9,124.7,124.3,76.8,73.8,71.3,31.7,20.8,17.3；HRMS(ESI-TOF):calc’d for C 19 H 20 NaO 3 [M+Na+]319.1304,found 319.1303.
Example 12: preparation of Compound J-12
The procedure was as in example 1 except that methyl 2-methyl-3-iodobenzoate (55.2 mg) was used as the iodide to give compound J-12 (pale yellow oily liquid, 72% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.82(d,J＝7.9Hz,1H),7.39–7.28(m,5H),7.13(d,J＝7.9Hz,1H),4.64–4.55(m,3H),3.91(s,3H),3.79(dd,J＝10.3,4.8Hz,1H),3.72(dd,J＝10.3,5.3Hz,1H),3.13(dd,J＝16.3,11.5Hz,1H),2.97(dd,J＝16.4,3.0Hz,1H),2.81(s,3H)；13C NMR(100MHz,CDCl 3 )δ168.3,163.7,143.6,143.2,137.8,133.9,132.9,128.7,128.1,128.0,125.7,125.1,76.5,73.9,71.0,52.5,32.0,18.7；HRMS(ESI-TOF):calc’d for C 20 H 20 NaO 5 [M+Na+]363.1205,found 363.1202.
Example 13: preparation of Compound J-13
The procedure was as in example 1 except that 2-methyl-4-fluoroiodobenzene (47.2 mg) was used as the iodide to give compound J-13 (pale yellow oily liquid, 79% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.38–7.27(m,5H),6.88(dd,J＝9.8,2.6Hz,1H),6.77(dd,J＝8.5,2.6Hz,1H),4.61–4.55(m,3H),3.77(dd,J＝10.3,4.7Hz,1H),3.70(dd,J＝10.3,5.2Hz,1H),3.10(dd,J＝16.3,11.5Hz,1H),2.91(dd,J＝16.3,3.1Hz,1H),2.66(s,3H)；13C NMR(100MHz,CDCl 3 )δ165.7,163.6,163.2,146.9(d,J＝9.5Hz),143.1(d,J＝9.7Hz),137.7,128.2(d,J＝73.2Hz),128.0,120.0(d,J＝2.8Hz),118.1(d,J＝21.3Hz),112.3(d,J＝21.6Hz),76.3,73.7,70.9,31.6,22.6(d,J＝1.4Hz)；19F NMR(377MHz,CDCl 3 )δ-105.5；HRMS(ESI-TOF):calc’d for C 18 H 17 FNaO 3 [M+Na+]323.1053,found 323.1048.
Example 14: preparation of Compound J-14
The procedure was as in example 1, except that 2-methyl-4-bromoiodobenzene (59.2 mg), palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol) and (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) were used as iodides to give compound J-14 (as a brown oily liquid in 50% yield.1H NMR (400 MHz, CDCl) 3 )δ7.36–7.23(m,6H),7.21(d,J＝4.8Hz,1H),4.60–4.50(m,3H),3.72(dd,J＝10.2,4.7Hz,1H),3.66(dd,J＝10.3,5.3Hz,1H),3.06(dd,J＝16.2,11.5Hz,1H),2.86(dd,J＝16.3,3.0Hz,1H),2.59(s,3H)；13C NMR(100MHz,CDCl 3 )δ163.9,145.2,141.7,137.8,134.2,128.7,128.5,128.1,127.9,127.7,122.7,76.5,73.8,71.0,31.3,22.2；HRMS(ESI-TOF):calc’d for C 18 H 17 BrNaO 3 [M+Na+]383.0253,found 383.0245.
Example 15: preparation of Compound J-15
The procedure was as in example 1 except that 2, 4-dimethyliodobenzene (46.4 mg) was used as the iodide to give compound J-15 (pale yellow oily liquid, 72% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.39–7.28(m,5H),7.00(s,1H),6.88(s,1H),4.62(s,2H),4.58(ddt,J＝11.7,5.1,2.6Hz,1H),3.78(dd,J＝10.2,4.8Hz,1H),3.70(dd,J＝10.3,5.3Hz,1H),3.06(dd,J＝16.1,11.6Hz,1H),2.88(dd,J＝16.1,3.0Hz,1H),2.63(s,3H),2.34(s,3H)；13C NMR(100MHz,CDCl 3 )δ164.6,143.7,143.1,140.1,137.9,132.1,128.6,128.0,127.9,126.2,121.0,76.6,73.8,71.3,31.5,22.3,21.6；HRMS(ESI-TOF):calc’d for C 19 H 20 NaO 3 [M+Na+]319.1304,found 319.1298.
Example 16: preparation of Compound J-16
The procedure was as in example 1 except that methyl 3-methyl-4-iodobenzoate (55.2 mg), palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol) and (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) were used as the iodide to give compound J-16 (white solid, 64% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.84(s,1H),7.73(s,1H),7.39–7.27(m,5H),4.66–4.57(m,3H),3.94(s,3H),3.78(dd,J＝10.3,4.8Hz,1H),3.72(dd,J＝10.3,5.2Hz,1H),3.15(dd,J＝16.2,11.4Hz,1H),3.00(dd,J＝16.2,3.1Hz,1H),2.71(s,3H)；13C NMR(100MHz,CDCl 3 )δ166.2,163.8,143.4,140.2,137.8,133.4,131.9,128.7,128.1,127.9,127.4,126.4,76.8,73.8,71.0,52.7,31.5,22.3；HRMS(ESI-TOF):calc’d for C 20 H 20 NaO 5 [M+Na+]363.1202,found 363.1193.
Example 17: preparation of Compound J-17
The procedure was as in example 1 except that 3-methyl-4-iodobenzamide (55.0 mg) was used as the iodide to give compound J-17 (white solid, 53% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.49(d,J＝6.2Hz,2H),7.39–7.27(m,5H),6.41(s,1H),4.65–4.54(m,3H),3.76(dd,J＝10.3,4.8Hz,1H),3.70(dd,J＝10.4,5.1Hz,1H),3.11(dd,J＝16.2,11.5Hz,1H),3.01(d,J＝4.9Hz,3H),2.95(dd,J＝16.3,3.1Hz,1H),2.66(s,3H)；13C NMR(100MHz,CDCl 3 )δ167.3,163.9,143.6,140.5,138.3,137.7,129.1,128.6,128.1,127.9,126.0,124.3,76.8,73.8,71.0,31.4,27.1,22.4；HRMS(ESI-TOF):calc’d for C 20 H 21 NNaO 4 [M+Na+]362.1362,found 362.1361.
Example 18: preparation of Compound J-18
The procedure was as in example 1 except that 2-methyl-5-fluoroiodobenzene (47.2 mg), palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol) and (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) were used as iodides to give compound J-18 (pale yellow oily liquid, 52% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.39–7.28(m,5H),7.15(d,J＝6.9Hz,2H),4.63(s,2H),4.59(m,1H),3.79(dd,J＝10.3,4.8Hz,1H),3.74(dd,J＝10.4,5.0Hz,1H),3.17(dd,J＝17.2,3.6Hz,1H),2.92(dd,J＝16.7,11.7Hz,1H),2.63(d,J＝1.2Hz,3H)；13C NMR(100MHz,CDCl 3 )δ163.6,158.4,156.0,138.7(d,J＝3.7Hz),137.8,131.7(d,J＝7.3Hz),128.3(d,J＝73.7Hz),128.1,126.8(d,J＝18.6Hz),124.8(d,J＝3.6Hz),119.6(d,J＝21.1Hz),76.6,73.9,71.1,24.1(d,J＝3.3Hz),21.8；19F NMR(377MHz,CDCl 3 )δ-122.0；HRMS(ESI-TOF):calc’d for C 18 H 17 FNaO 3 [M+Na+]323.1053,found 323.1048.
Example 19: preparation of Compound J-19
The procedure was as in example 1 except that 2-chloro-3, 4-dimethoxyiodobenzene (59.6 mg), palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol) and (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) were used as iodides to give compound J-19 (white solid, 49% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.40–7.27(m,5H),6.66(s,1H),4.64–4.53(m,3H),3.93(s,3H),3.85(s,3H),3.78(dd,J＝10.2,4.7Hz,1H),3.70(dd,J＝10.2,5.6Hz,1H),3.08(dd,J＝16.2,11.5Hz,1H),2.92(dd,J＝16.2,3.0Hz,1H)；13C NMR(100MHz,CDCl 3 )δ161.5,157.3,146.1,138.1,137.8,131.7,128.6,128.1,127.9,115.9,109.1,76.3,73.8,70.9,60.8,56.4,31.9；HRMS(ESI-TOF):calc’d for C 19 H 19 ClNaO 5 [M+Na+]385.0813,found 385.0808.
Example 20: preparation of Compound J-20
The procedure was as in example 1 except that 1-iodonaphthalene (50.8 mg) was used as the iodide to give compound J-20 (white solid, 67% yield). 1H NMR (400 MHz, CDCl) 3 )δ9.21(d,J＝8.7Hz,1H),7.99(d,J＝8.3Hz,1H),7.85(d,J＝8.1Hz,1H),7.66(ddd,J＝8.6,6.8,1.4Hz,1H),7.54(t,J＝7.5Hz,1H),7.37(d,J＝4.4Hz,4H),7.32(dd,J＝8.5,4.3Hz,2H),4.70(dd,J＝12.0,3.0Hz,1H),4.66–4.61(m,2H),3.85(dd,J＝10.3,4.8Hz,1H),3.79(dd,J＝10.3,5.2Hz,1H),3.31(dd,J＝16.6,11.8Hz,1H),3.06(dd,J＝16.6,3.1Hz,1H)；13C NMR(100MHz,CDCl 3 )δ164.3,140.8,137.8,134.8,133.3,132.0,129.0,128.7,128.6,128.0,127.9,126.4,126.3,125.2,120.1,76.2,73.8,71.1,31.9；HRMS(ESI-TOF):calc’d for C 21 H 18 NaO 3 [M+Na+]341.1148,found 341.1138.
Example 21: preparation of Compound J-21
The procedure was as in example 1 except that 4-bromo-1-iodonaphthalene (66.4 mg), palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol) and (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) were used as iodides to give compound J-21 (as a tan solid, 45% yield). 1H NMR (400 MHz, CDCl) 3 )δ9.22(d,J＝8.1Hz,1H),8.31(d,J＝8.3Hz,1H),7.75–7.67(m,2H),7.64(ddd,J＝8.2,6.8,1.3Hz,1H),7.40–7.27(m,5H),4.75–4.60(m,3H),3.84(dd,J＝10.3,4.7Hz,1H),3.79(dd,J＝10.3,5.3Hz,1H),3.31(dd,J＝16.6,11.7Hz,1H),3.05(dd,J＝16.7,3.1Hz,1H)；13C NMR(100MHz,CDCl 3 )δ163.8,140.7,137.8,133.1,131.9,130.6,129.8,129.4,128.7,128.1,128.0,127.9,127.8,126.9,120.1,76.1,73.9,70.9,31.6；HRMS(ESI-TOF):calc’d for C 21 H 17 BrNaO 3 [M+Na+]419.0253,found 419.0245.
Example 22: preparation of Compound J-22
The procedure was as in example 1 except that 1-iodopyrene (65.6 mg) was used as the iodide to give compound J-22 (yellow solid, 58% yield). 1H NMR (400 MHz, CDCl) 3 )δ9.52(d,J＝9.5Hz,1H),8.32–8.22(m,3H),8.21–8.16(m,1H),8.06(t,J＝7.6Hz,1H),8.02–7.97(m,1H),7.94(d,J＝2.4Hz,1H),7.38(d,J＝6.6Hz,5H),4.81(ddd,J＝9.6,5.3,2.6Hz,1H),4.68(s,2H),3.90(d,J＝4.8Hz,1H),3.87–3.82(m,1H),3.54(dd,J＝16.0,11.5Hz,1H),3.36(dt,J＝16.1,2.4Hz,1H)；13C NMR(100MHz,CDCl 3 )δ165.0,137.9,137.7,135.1,132.7,131.0,130.8,130.6,130.3,128.7,128.1,128.0,127.0(127.05,126.99),126.8,126.6,125.4,124.5,124.1,123.4,117.3,76.8,73.9,71.3,32.5；HRMS(ESI-TOF):calc’d for C 27 H 20 NaO 3 [M+Na+]415.1304,found 415.1299.
Example 23: preparation of Compound J-23
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The procedure was as in example 1 except that iodobenzene (40.8 mg), palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol) and (1S, 2S, 4S) -2-norbornene-5, 6-oxamide biphenyl (31.5 mg,0.5 mmol) were used as the iodide to give compound J-23 (colorless oily liquid, 47% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.42(t,J＝7.6Hz,1H),7.40–7.21(m,11H),7.12(d,J＝7.5Hz,1H),4.61(d,J＝10.1Hz,5H),4.04(s,1H),3.78(dd,J＝10.4,5.0Hz,1H),3.72(dd,J＝10.4,5.1Hz,1H),3.64–3.48(m,3H),3.31(dd,J＝13.3,3.8Hz,1H),3.24–3.07(m,2H),2.93(dd,J＝16.2,2.9Hz,1H)；13C NMR(100MHz,CDCl 3 )δ165.8,143.7,140.2,138.4,137.8,133.3,131.7,128.6,128.5,128.0,127.9(127.91,127.89),127.8,126.2,124.1,77.1,74.8,73.8,73.5,72.6,71.0,38.4,31.6；HRMS(ESI-TOF):calc’d for C 27 H 28 NaO 5 [M+Na+]455.1828,found 455.1823；[α]23D:-66.739(c＝0.92,CHCl 3 ).
Example 24: preparation of Compound J-24
The procedure was as in example 1 except that iodide 4-chloroiodobenzene (47.6 mg), palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol) and (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) were used to give compound J-24 (colorless oily liquid, 42% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.50–7.26(m,11H),7.13(s,1H),4.69–4.50(m,5H),4.10–3.97(m,1H),3.74(qd,J＝10.4,5.0Hz,2H),3.57(p,J＝9.5Hz,2H),3.40–3.26(m,2H),3.21–3.07(m,2H),2.91(dd,J＝16.3,2.9Hz,1H)；13C NMR(100MHz,CDCl 3 )δ165.0,145.8,141.9,139.4,138.3,137.7,131.8,128.7,128.6,128.1,127.9,127.9,126.3,122.6,74.6,73.9,73.6,72.3,70.8,38.3,31.5；HRMS(ESI-TOF):calc’d for C 27 H 27 ClNaO 5 [M+Na+]489.1439,found 489.1427；[α]23D:-71.111(c＝0.81,CHCl3).
Example 25: preparation of Compound J-25
The procedure is as in example 1, except that the iodide used is(81.0 mg), palladium acetate (4.5 mg,0.1 mm)ol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol), (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) to give compound J-25 (colorless oily liquid, 35% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.42–7.26(m,10H),7.05(s,1H),6.92(s,1H),5.03(d,J＝8.3Hz,1H),4.69–4.50(m,6H),3.99(s,1H),3.77(dd,J＝10.3,4.8Hz,1H),3..72(m,4H),3.62–3.54(m,2H),3.50(d,J＝5.4Hz,1H),3.33(dd,J＝13.2,3.4Hz,1H),3.18–3.05(m,3H),2.98(dd,J＝13.6,6.7Hz,1H),2.88(dd,J＝16.2,2.9Hz,1H),1.40(s,9H)；13C NMR(100MHz,CDCl 3 )δ172.0,165.6,155.1,143.9,142.1,140.5,138.4,137.8,132.9,128.6,128.5,128.0,127.9,127.8,127.1,122.7,80.3,77.0,74.8,73.8,73.5,72.6,71.0,54.2,52.6,38.5,31.6,28.4；HRMS(ESI-TOF):calc’d for C 36 H 43 NNaO 9 [M+Na+]634.3007,found 634.3010；[α]23D:-40.349(c＝0.86,CHCl3).
Example 26: preparation of Compound J-26
The procedure was as in example 1 except that 2-methyl iodobenzene (43.6 mg) was used as the iodide and (methoxymethyl) oxirane (52.9 mg) was used as the epoxide to give compound J-26 (colorless oily liquid, 49% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.36(t,J＝7.6Hz,1H),7.19(d,J＝8.4Hz,1H),7.08(d,J＝7.5Hz,1H),4.56(dtd,J＝11.7,5.1,3.0Hz,1H),3.69(dd,J＝10.3,5.0Hz,1H),3.62(dd,J＝10.3,5.1Hz,1H),3.44(s,3H),3.08(dd,J＝16.1,11.7Hz,1H),2.90(dd,J＝16.1,2.9Hz,1H),2.66(s,3H)；13C NMR(100MHz,CDCl 3 )δ164.4,143.2,140.0,132.9,131.2,125.5,123.7,76.5,73.8,59.7,31.4,22.3；HRMS(ESI-TOF):calc’d for C 12 H 14 NaO 3 [M+Na+]229.0835,found 229.0831.
Example 27: preparation of Compound J-27
The procedure was as in example 1 except that 2-methyl iodobenzene (43.6 mg) was used as the iodide and propylene oxide (34.9 mg) was used as the epoxy compound to give compound J-27 (pale yellow oily liquid, 60% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.35(t,J＝7.6Hz,1H),7.18(d,J＝7.7Hz,1H),7.05(d,J＝7.5Hz,1H),4.56(ddp,J＝12.5,6.3,3.1Hz,1H),2.93(dd,J＝16.0,10.9Hz,1H),2.86(dd,J＝16.0,3.5Hz,1H),2.67(s,3H),1.48(d,J＝6.3Hz,3H)；13C NMR(100MHz,CDCl 3 )δ165.2,143.1,140.4,132.7,131.2,125.3,123.8,74.5,36.3,22.3,20.9；HRMS(ESI-TOF):calc’d for C 11 H 12 NaO 2 [M+Na+]199.0729,found 199.0724.
Example 28: preparation of Compound J-28
The procedure was as in example 1 except that 2-methyl iodobenzene (43.6 mg) was used as the iodide and phenyl glycidyl ether (90.1 mg) as the epoxy compound to give compound J-28 (white solid, 70% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.40(t,J＝7.6Hz,1H),7.30(dd,J＝8.7,7.3Hz,2H),7.22(d,J＝7.7Hz,1H),7.13(d,J＝7.5Hz,1H),6.99(t,J＝7.4Hz,1H),6.96–6.90(m,2H),4.80(dddd,J＝11.1,5.9,4.7,3.2Hz,1H),4.29(dd,J＝9.9,4.7Hz,1H),4.18(dd,J＝9.9,5.9Hz,1H),3.21(dd,J＝16.1,11.3Hz,1H),3.09(dd,J＝16.1,3.2Hz,1H),2.69(s,3H)；13C NMR(100MHz,CDCl 3 )δ164.2,158.4,143.3,139.7,133.1,131.4,129.8,125.6,123.7,121.6,114.7,75.7,68.8,31.6,22.4；HRMS(ESI-TOF):calc’d for C 17 H 16 NaO 3 [M+Na+]291.0991,found 291.0988.
Example 29: preparation of Compound J-29
The procedure is as in example 1, except that the iodide used is 2-methyliodide(43.6 mg) and glycidol (44.5 mg) were added to the reaction mixture to give compound J-29 (colorless oily liquid, 59% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.38(t,J＝7.6Hz,1H),7.20(d,J＝7.6Hz,1H),7.10(d,J＝7.5Hz,1H),4.57–4.51(m,1H),3.94(m,1H),3.83(m,1H),3.18(dd,J＝16.1,12.4Hz,1H),2.81(dd,J＝16.1,2.8Hz,1H),2.67(s,3H),2.30–2.23(m,1H)；13C NMR(100MHz,CDCl 3 )δ164.7,143.3,140.1,133.1,131.3,125.6,123.5,78.5,64.4,30.5,22.4；HRMS(ESI-TOF):calc’d for C 11 H 12 NaO 3 [M+Na+]215.0678,found 215.0672.
Example 30: preparation of Compound J-30
The procedure was as in example 1 except that 2-methyl iodobenzene (43.6 mg) was used as the iodide and glycidyl butyl ester (86.5 mg) as the epoxy compound, to give compound J-30 (colorless oily liquid, 65% yield, 98% ee). 1H NMR (400 MHz, CDCl) 3 )δ7.38(t,J＝7.6Hz,1H),7.21(d,J＝7.6Hz,1H),7.08(d,J＝7.5Hz,1H),4.66(dtd,J＝11.6,4.8,3.1Hz,1H),4.34(dd,J＝4.8,1.1Hz,2H),3.07(dd,J＝15.9,11.6Hz,1H),2.89(dd,J＝16.1,3.1Hz,1H),2.67(s,3H),2.34(t,J＝7.4Hz,2H),1.72–1.64(m,2H),0.95(t,J＝7.4Hz,3H)；13C NMR(100MHz,CDCl 3 )δ173.5,164.1,143.4,139.4,133.1,131.5,125.5,123.5,75.4,64.9,36.1,31.1,22.3,18.5,13.8；HRMS(ESI-TOF):calc’d for C 15 H 18 NaO 4 [M+Na+]285.1097,found 285.1093.
Example 31: preparation of Compound J-31
The procedure is as in example 1, except that 2-methyliodide (43.6 mg) is used as the iodide, 1, 2-epoxydodecane (110.6 mg) is used as the epoxide, palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmo)l), (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) to give compound J-31 (white solid, 77% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.35(t,J＝7.6Hz,1H),7.18(d,J＝7.6Hz,1H),7.05(d,J＝7.5Hz,1H),4.40(dddd,J＝10.9,7.4,5.3,3.2Hz,1H),2.93(dd,J＝16.0,11.1Hz,1H),2.84(dd,J＝16.0,3.2Hz,1H),2.67(s,3H),1.85(m,1H),1.68(m,1H),1.44(m,1H),1.28(d,J＝12.1Hz,15H),0.88(t,J＝6.7Hz,3H)；13C NMR(100MHz,CDCl 3 )δ165.3,143.0,140.5,132.7,131.1,125.3,124.1,78.2,35.0,34.7,32.1,29.8,29.7,29.7,29.6,29.5,25.1,22.9,22.3,14.3；HRMS(ESI-TOF):calc’d for C 20 H 30 NaO 2 [M+Na+]325.2138,found 325.2134.
Example 32: preparation of Compound J-32
The procedure was as in example 1 except that 2-methyl iodobenzene (43.6 mg) was used as the iodide, 1, 2-epoxyoctadecane (160.0 mg) as the epoxy compound, palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol) and (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) to give compound J-32 (white solid, 60% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.35(t,J＝7.6Hz,1H),7.18(d,J＝7.6Hz,1H),7.05(d,J＝7.5Hz,1H),4.45–4.35(m,1H),2.93(dd,J＝16.0,11.2Hz,1H),2.84(dd,J＝16.0,3.2Hz,1H),2.67(s,3H),1.85(m,1H),1.68(m,1H),1.44(m,1H),1.26(s,27H),0.88(t,J＝6.7Hz,3H)；13C NMR(100MHz,CDCl 3 )δ165.3,143.0,140.5,132.7,131.2,125.3,124.1,78.2,35.0,34.7,32.1,29.9(29.88),29.8(29.85),29.8(29.83),29.8(29.75),29.7,29.6(29.60),29.6(29.55),25.2,22.9,22.3,14.3；HRMS(ESI-TOF):calc’d for C 26 H 42 NaO 2 [M+Na+]409.3077,found 409.3070.
Example 33: preparation of Compound J-33
The procedure was as in example 1, except that 2-methyl iodobenzene (43.6 mg) was used as the iodide, epichlorohydrin (55.5 mg) as the epoxy compound, palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol), (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) to give compound J-33 (colorless oily liquid, 61% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.40(t,J＝7.6Hz,1H),7.22(d,J＝7.6Hz,1H),7.11(d,J＝7.5Hz,1H),4.64(ddt,J＝10.7,6.7,4.4Hz,1H),3.81(dd,J＝11.5,4.7Hz,1H),3.71(dd,J＝11.5,6.7Hz,1H),3.16–3.04(m,2H),2.67(s,3H)；13C NMR(100MHz,CDCl 3 )δ163.8,143.4,139.1,133.2,131.5,125.7,123.4,76.6,44.8,32.0,22.3；HRMS(ESI-TOF):calc’d for C 11 H 11 ClNaO 2 [M+Na+]233.0339,found 233.0335.
Example 34: preparation of Compound J-34
The procedure was as in example 1 except that 2-methyl iodobenzene (43.6 mg) was used as the iodide, 4-epoxypropoxycarbazole (143.5 mg) as the epoxy compound, palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol) and (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) were used to give compound J-34 (white solid, 72% yield). 1H NMR (400 MHz, CDCl) 3 )δ8.26(d,J＝7.8Hz,1H),8.12(s,1H),7.46–7.37(m,3H),7.34(t,J＝8.0Hz,1H),7.23(dd,J＝9.3,2.7Hz,1H),7.16(d,J＝7.5Hz,1H),7.09(d,J＝8.1Hz,1H),6.69(d,J＝8.0Hz,1H),5.02(ddt,J＝10.8,6.8,3.8Hz,1H),4.58(dd,J＝9.9,4.4Hz,1H),4.46(dd,J＝9.9,6.2Hz,1H),3.39(dd,J＝16.1,11.3Hz,1H),3.25(dd,J＝16.1,3.2Hz,1H),2.73(s,3H)；13C NMR(100MHz,CDCl 3 )δ164.3,154.8,143.4,141.2,139.7,138.9,133.1,131.5,126.8,125.8,125.3,123.8,123.2,122.6,120.0,112.9,110.3,104.4,101.3,75.8,68.9,32.0,22.4；HRMS(ESI-TOF):calc’d for C 23 H 19 NNaO 3 [M+Na+]380.1257,found 380.1252.
Example 35: preparation of Compound J-35
The procedure was as in example 1 except that 2-methyl iodobenzene (43.6 mg) was used as the iodide, N- (2, 3-epoxypropyl) phthalamide (121.9 mg) as the epoxy compound, palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol) and (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) as the epoxy compound to give compound J-35 (white solid, 56% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.86(dd,J＝5.4,3.1Hz,2H),7.73(dd,J＝5.5,3.0Hz,2H),7.34(t,J＝7.6Hz,1H),7.17(d,J＝7.6Hz,1H),7.05(d,J＝7.5Hz,1H),4.80(qd,J＝6.9,5.5Hz,1H),4.13(dd,J＝14.1,7.3Hz,1H),3.91(dd,J＝14.1,5.6Hz,1H),3.02(d,J＝6.7Hz,2H),2.64(s,3H)；13C NMR(100MHz,CDCl 3 )δ168.2,163.7,143.3,139.0,134.4,133.0,132.0,131.4,125.6,123.8,123.7,74.4,41.1,32.3,22.3；HRMS(ESI-TOF):calc’d for C 19 H 15 NNaO 4 [M+Na+]344.0893,found 344.0889.
Example 36: preparation of Compound J-36
The procedure is as in example 1, except that the iodide used is 2-methyliodide (43.6 mg), epoxide as shown(241.2 mg), palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol), (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) to give compound J-36 (colorless oily liquid, 51% yield). 1H NMR (400 MHz, CDCl) 3 )δ7.40(t,J＝7.6Hz,1H),7.22(d,J＝7.7Hz,1H),7.10(d,J＝7.5Hz,1H),5.78(s,1H),5.12(s,1H),4.98(s,1H),4.78–4.66(m,2H),4.39(q,J＝6.2,5.2Hz,2H),4.27(t,J＝6.1Hz,1H),3.31(dd,J＝6.2,2.7Hz,1H),3.10(dd,J＝16.1,11.4Hz,2H),2.93(dd,J＝16.0,3.1Hz,1H),2.65(s,4H),2.61(d,J＝4.8Hz,2H),2.29(d,J＝16.3Hz,1H),1.93(d,J＝8.8Hz,2H),1.73(dq,J＝12.9,6.2Hz,2H),1.56(d,J＝11.6Hz,2H),1.41(d,J＝11.0Hz,1H),1.23(s,4H)；13C NMR(100MHz,CDCl 3 )δ177.0,174.4,164.1,153.5,151.9,143.5,139.1,133.3,131.6,125.6,123.3,,114.0,107.3,79.0,75.5,75.0,73.9,65.2,49.6,49.2,48.6,48.6,46.0,45.7,39.2,37.1,31.0,22.4,18.9,17.2；HRMS(ESI-TOF):calc’d for C 30 H 33 NaO 8 [M+Na+]543.2018,found 543.2013.
Example 37: preparation of Compound J-37
The procedure was as in example 1 except that 2-benzyloxy-4-methoxyiodobenzene (68.0 mg) was used as the iodide, and S-propylene oxide (34.9 mg), palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol), (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) was used as the epoxide to give compound J-37 (colorless oily liquid, 45% yield, 99% ee). 1H NMR (400 MHz, CDCl) 3 )δ7.54(d,J＝7.1Hz,2H),7.37(t,J＝7.6Hz,2H),7.30(d,J＝7.3Hz,1H),6.43(d,J＝2.3Hz,1H),6.30(s,1H),5.29–5.16(m,2H),4.53(dqd,J＝12.5,6.2,3.1Hz,1H),3..80(s,3H),2.88(dd,J＝16.0,11.0Hz,1H),2.79(dd,J＝16.0,3.2Hz,1H),1.47(d,J＝6.3Hz,3H)；13C NMR(100MHz,CDCl 3 )δ164.3,162.6,162.2,144.0,136.6,128.8,127.9,126.8,107.7,104.5,99.7,73.7,70.7,55.6,36.8,20.9；HRMS(ESI-TOF):calc’d for C 18 H 18 NaO 4 [M+Na+]321.1097,found 321.1091；HPLC:Daicel Chiralpak OD column,20％iPrOH in nhexane,1mL/min,λ＝230nm,tR(major)＝13.763min,tR(minor)＝16.379min；[α]25D:65.172(c＝0.29,CHCl3).
Example 38: preparation of Compound J-38
The procedure was as in example 1, except that 2-benzyloxyiodobenzene (62.0 mg) was used as the iodide, and R-propylene oxide (34.9 mg), palladium acetate (4.5 mg,0.1 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (23.0 mg,0.24 mmol), and (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl (31.5 mg,0.5 mmol) were used as the epoxy compound to give compound J-38 (colorless oily liquid, 55% yield, 99% ee). 1H NMR (400 MHz, CDCl) 3 )δ7.54(d,J＝7.5Hz,2H),7.42–7.33(m,3H),7.29(d,J＝7.3Hz,1H),6.93(d,J＝8.4Hz,1H),6.79(d,J＝7.5Hz,1H),5.33–5.19(m,2H),4.56(m,1H),2.96–2.81(m,2H),1.48(d,J＝6.3Hz,3H)；13C NMR(100MHz,CDCl 3 )δ162.6,160.2,142.2,136.7,134.4,128.7,127.9,126.8,119.7,114.6,113.0,74.2,70.7,36.3,20.8；HRMS(ESI-TOF):calc’d for C 17 H 16 NaO 3 [M+Na+]291.0991,found291.0988；HPLC:Daicel Chiralpak AD column,25％iPrOH in nhexane,1mL/min,λ＝290nm,tR(major)＝15.721min,tR(minor)＝10.234min；[α]25D:-145.83(c＝0.24,CHCl3).
Example 39: preparation of Compound J-39
Palladium acetate (4.5 mg,0.02 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (19.1 mg,0.04 mmol) and dried N-methylpyrrolidone (0.5 mL) were added to a 10 mL-port reaction tube which was dried and equipped with a magnetic stirrer, and after half an hour of pre-stirring of the catalyst and ligand, potassium carbonate (27.6 mg,0.2 mmol) and 2-norbornene-5, 6-ethanediamide quinoline (29.4 mg,0.1 mmol) were added. 1-iodonaphthalene (50.8 mg,0.2 mmol) and benzyl glycidyl ether (98.5 mg,0.6 mmol) were added and the reaction tube was connected to CO: the mixed gas balloon with Ar=1:7 is placed in a reaction plate at 60 ℃ and heated and stirred for 16 hours. Extracting the reaction solution with ethyl acetate and water, back-extracting the water phase for three times, and collectingThe organic phase was washed three times with saturated sodium chloride, the organic phase was dried over anhydrous sodium sulfate, the solvent was removed by distillation under reduced pressure, and the compound J-39 (pale yellow solid, 90% yield) was isolated and purified by column chromatography to give 1H NMR (400 MHz, CDCl) 3 ):δ9.21(d,J＝8.7Hz,1H),8.00(d,J＝8.3Hz,1H),7.85(dd,J＝8.2,1.4Hz,1H),7.66(ddd,J＝8.5,6.9,1.5Hz,1H),7.54(ddd,J＝8.1,6.8,1.2Hz,1H),7.37(d,J＝4.4Hz,4H),7.33(d,J＝2.2Hz,1H),4.76–4.58(m,3H),3.89–3.75(m,2H),3.31(dd,J＝16.6,11.8Hz,1H),3.07(dd,J＝16.6,3.1Hz,1H).13C NMR(100MHz,CDCl 3 ):δ164.24,140.73,137.79,134.82,133.27,131.99,128.94,128.66,128.59,127.98,127.89,126.38,126.31,125.17,120.07,76.16,73.81,71.07,31.88.HRMS(ESI-TOF):calc’d for C 21 H 19 O 3 [M+H+]319.1329,found 319.1339。
Example 40: preparation of Compound J-40
The procedure was as in example 39, except that glycidol (44.5 mg) was used as the epoxy compound, (methoxymethyl) oxirane (52.9 mg) to give compound J-40 (colorless oily liquid, 80% yield). 1H NMR (400 MHz, CDCl) 3 ):δ9.18(d,J＝8.7Hz,1H),8.01(d,J＝8.3Hz,1H),7.86(dd,J＝8.1,1.4Hz,1H),7.66(ddd,J＝8.6,6.8,1.5Hz,1H),7.54(ddd,J＝8.0,6.8,1.2Hz,1H),7.33(d,J＝8.3Hz,1H),4.64(ddt,J＝12.6,5.1,3.2Hz,1H),4.02(dd,J＝12.3,3.4Hz,1H),3.89(dd,J＝12.3,5.0Hz,1H),3.40(dd,J＝16.6,12.6Hz,1H),2.94(dd,J＝16.6,2.9Hz,1H),2.49(s,1H).13C NMR(100MHz,CDCl 3 ):δ163.51,139.91,134.05,132.30,131.00,128.07,127.73,125.49,125.24,124.21,118.81,76.99,63.17,59.54,29.88,20.18,13.31,0.14.HRMS(ESI-TOF):calc’d for C 14 H 13 O 3 [M+H+]229.0859,found 229.0855.
Example 41: preparation of Compound J-41
The procedure was as in example 39, except that (methoxymethyl) oxirane (52.9 mg) was used as the epoxide compound to give compound J-41 (colorless oily liquid, 74% yield). 1H NMR (400 MHz, CDCl) 3 ):δ9.19(dd,J＝8.7,1.1Hz,1H),7.98(d,J＝8.3Hz,1H),7.90–7.82(m,1H),7.65(ddd,J＝8.6,6.8,1.5Hz,1H),7.52(ddd,J＝8.1,6.9,1.2Hz,1H),7.31(d,J＝8.3Hz,1H),4.65(dtd,J＝11.9,4.9,3.1Hz,1H),3.72(qd,J＝10.3,4.9Hz,2H),3.46(s,3H),3.28(dd,J＝16.6,11.9Hz,1H),3.03(dd,J＝16.6,3.1Hz,1H).13C NMR(100MHz,CDCl 3 ):δ164.19,140.71,134.81,133.26,131.97,128.92,128.65,126.38,126.30,125.15,120.02,76.03,73.54,59.65,31.72.HRMS(ESI-TOF):calc’d for C 15 H 15 O 3 [M+H+]343.1016,found 343.1017.
The present invention is not limited to the above-mentioned embodiments, but any modifications, equivalents, improvements and modifications within the scope of the invention will be apparent to those skilled in the art.

Claims (2)

1. A method for synthesizing isochromanone compounds based on carbon monoxide gas or carbon monoxide substitution source, which is characterized by comprising the following steps:
under the atmosphere of protective gas, aryl iodide A, epoxy compound B and carbon monoxide gas C or carbon monoxide substitution source K are used as starting materials, under the action of palladium catalyst D, phosphine ligand E, norbornene derivative F and alkali G, stirring and reacting in organic solvent I until the reaction is completed, and separating reactants after the reaction is completed to obtain the heterochromatic ketone compound shown in formula J; wherein when carbon monoxide is the starting material, carbon monoxide is dissolved in solvent M and base L is added to produce carbon monoxide;
the reaction equation is as follows:
wherein R is 1 Is one or more of alkyl, aryl, ester, alkoxy, benzyloxy, tert-butyloxycarbonyl and halogen; r is R 2 Is one of alkyl, aryl, ester, hydroxyl, alkoxy, phenoxy, benzyloxy, oxy carbazole and phthalic acid amide; x represents R 1 X is more than or equal to 0 and less than or equal to 3, R 1 The substitution position on the aromatic ring is defined by the 2-4 position;
the carbon monoxide gas C is a mixed gas of carbon monoxide and inert gas, and the mixing volume ratio is any one of 1:1 to 1:20;
the norbornene derivative F is 2-norbornene-5-formanilide, (1S, 2S, 4S) -2-norbornene-5, 6-ethanediamide biphenyl or 2-norbornene-5, 6-ethanediamide quinoline;
the palladium catalyst D is Pd (PPh) 3 ) 4 、Pd(dba) 2 、Pd 2 (dba) 3 、Pd(OAc) 2 、Pd(PhCN) 2 Cl 2 、Pd(MeCN) 2 Cl 2 、PdCl 2 、PdI 2 、[Pd(allyl)Cl] 2 Any one or more of the following;
the phosphine ligand E is 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl;
the alkali G is potassium acetate or potassium carbonate;
the solvent I is N-methyl pyrrolidone;
the base L is triethylamine;
the solvent M is 1, 4-dioxane.
2. The method according to claim 1, characterized in that: the reaction temperature is 40-100 ℃.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3935236A (en) * 1973-05-30 1976-01-27 Gruppo Lepetit, S.P.A. Aminopropanol substituted isochromanones and phthalides
JPH11263787A (en) * 1998-03-13 1999-09-28 Japan Science & Technology Corp Production of isochromanone derivative
CN101928244A (en) * 2010-07-13 2010-12-29 中国药科大学 Structural analogue and derivative of isochromanone-4 compound with cardiovascular activity, preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3935236A (en) * 1973-05-30 1976-01-27 Gruppo Lepetit, S.P.A. Aminopropanol substituted isochromanones and phthalides
JPH11263787A (en) * 1998-03-13 1999-09-28 Japan Science & Technology Corp Production of isochromanone derivative
CN101928244A (en) * 2010-07-13 2010-12-29 中国药科大学 Structural analogue and derivative of isochromanone-4 compound with cardiovascular activity, preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Electron-Transfer-Induced Intramolecular Heck Carbonylation Reactions Leading to Benzolactones and Benzolactams";Fukuyama, Takahide 等;《Synthesis 》;第50卷(第15期);第3015-3021页 *
"钯/降冰片烯/手性氨基酸协同催化立体选择性构建全碳桥环分子骨架";叶金祥 等;《有机化学》;第42卷(第01期);第307-309页 *
"降冰片烯诱导下的钯催化苯环间位芳基化偶联反应研究";邱杨成;《中国优秀硕士论文全文数据库（电子期刊）工程科技I辑》(第11期);第B014-13页 *
Cheng, Guolin 等."Practical Pd(II)-Catalyzed C-H Alkylation with Epoxides: One-Step Syntheses of 3,4-Dihydroisocoumarins".《Journal of the American Chemical Society》.2015,第137卷(第34期),第10950-10953页. *

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