CN116003369A - 3-spirohexenone substituted chroman structure and synthesis method thereof - Google Patents
3-spirohexenone substituted chroman structure and synthesis method thereof Download PDFInfo
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- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical group C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 230000000975 bioactive effect Effects 0.000 claims abstract description 11
- -1 p-methylene quinone derivative Chemical class 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 7
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007848 Bronsted acid Substances 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 48
- 239000000047 product Substances 0.000 description 27
- 239000002994 raw material Substances 0.000 description 26
- 239000000126 substance Substances 0.000 description 24
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 description 9
- 239000003814 drug Substances 0.000 description 6
- 238000010276 construction Methods 0.000 description 5
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 3
- 239000000546 pharmaceutical excipient Substances 0.000 description 3
- 239000012264 purified product Substances 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000009509 drug development Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008194 pharmaceutical composition Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 1
- FXWFZIRWWNPPOV-UHFFFAOYSA-N 2-aminobenzaldehyde Chemical compound NC1=CC=CC=C1C=O FXWFZIRWWNPPOV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000003016 chromanyl group Chemical group O1C(CCC2=CC=CC=C12)* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- KVRSDIJOUNNFMZ-UHFFFAOYSA-L nickel(2+);trifluoromethanesulfonate Chemical compound [Ni+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F KVRSDIJOUNNFMZ-UHFFFAOYSA-L 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000000651 prodrug Substances 0.000 description 1
- 229940002612 prodrug Drugs 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a 3-spirohexenone substituted chroman bioactive framework and a synthesis method thereof. The structural formula of the 3-spirohexenone substituted chroman bioactive framework is as follows:
wherein R1 is any one of a hydrogen atom, a methyl group and a tert-butyl group; r2 is any one of alkenyl and aryl; r3 is any one of isopropyl and tert-butyl. The invention provides a synthesis method thereof, which comprises the following steps: the p-methylene quinone derivative and the catalyst are mixed homogeneously in solvent and reacted at rt-100 deg.c. The invention provides a method for efficiently synthesizing 3-spirohexenone substituted chroman compounds with various structures, which realizes the efficient synthesis of bioactive molecules with 3-spirohexenone substituted chroman structures based on a hydrogen migration strategy for the first time.
Description
Technical Field
The invention relates to the technical field of pharmaceutical intermediates and chemical synthesis, in particular to a 3-spirohexenone substituted chroman structure with bioactivity, and a synthesis method and application thereof.
Background
The chroman and cyclohexenone are core structures of a plurality of natural products, medicines and medicine intermediates, are structural fragments with important medicine activity, develop a green synthesis technology to efficiently construct two active frameworks, and effectively splice the two active frameworks to prepare a novel thick and doped compound, and have extremely important significance for developing novel medicine molecules and promoting the development of medicine health industry.
For example, in 2018, li Shuaishuai teaches that phenol and o-aminobenzaldehyde are used as starting materials through a hydrogen migration strategy, so that the dearomatization of phenol is quickly and efficiently realized under the room temperature condition in a hexafluoroisopropanol system, a spirohexenone framework is constructed, and a green and economical method is provided for the conversion of phenol into a spirohexenone framework with high added value (chem. Sci.2018,9, 8253-8259).
In 2022, li Shuaishuai teaches that indole and o-alkoxy benzaldehyde which are cheap and easily available are used as starting materials, the dearomatization of indole is rapidly and efficiently realized in a hexafluoroisopropanol system at room temperature to 100 ℃, a spiro indolenine fused chromane skeleton is constructed, and a new strategy is provided for the construction of the spiro chromane skeleton (org.chem. Front.2022,9, 1668-1674).
Although there are many reports on efficient construction methods of cyclohexenone and chroman skeletons, there are few reports on efficient construction methods of cyclohexenone thick and variegated chroman skeletons by splicing two active structures. In view of the physiological and pharmacological activities of the cyclohexenone and chroman structures, the development of a high-efficiency one-step synthesis molecule containing the two active structures has important significance for developing novel medicines.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a 3-spirohexenone substituted chroman structure with bioactivity, and a synthesis method and application thereof. The novel 3-spirohexenone substituted chroman bioactive skeleton provided by the invention provides a novel model molecule for drug development. The invention provides a synthesis method of a 3-spirohexenone substituted chroman bioactive framework, which is simple to operate, efficient and practical, and the constructed framework contains various functional groups, so that the later synthesis and application of the framework are facilitated.
The technical scheme of the invention is realized as follows:
the structural formula of the 3-spirohexenone substituted chroman bioactive skeleton is shown as follows:
wherein R is 1 Is any one of hydrogen atom, methyl and tertiary butyl; r is R 2 Is any one of alkenyl and aryl; r is R 3 Is either isopropyl or tert-butyl.
The compounds of the present invention may exist in the form of one or more stereoisomers. The various isomers include tautomers, geometric isomers, enantiomers, diastereomers and the like. These isomers and mixtures of these isomers are all within the scope of the present invention.
Based on the same inventive concept, the invention also provides a synthesis method of the 3-spirohexenone substituted chroman bioactive skeleton, which comprises the following steps:
uniformly mixing a p-methylene quinone derivative and a catalyst in a solvent, and reacting at rt-100 ℃ to prepare a 3-spirohexenone substituted chroman compound;
wherein the structural formula of the p-methylenequinone derivative is shown as follows:
wherein R is 1 Is any one of hydrogen atom, methyl and tertiary butyl; r is R 2 Is any one of alkenyl and aryl; r is R 3 Is either isopropyl or tert-butyl.
The reaction condition can be detected by thin layer chromatography, and the purification is carried out after the reaction is finished, so as to obtain the purified product of the 3-spirohexenone substituted chroman compound.
The reaction process specifically comprises the following steps:
the p-methylene quinone derivative initiates intramolecular [1,5] -hydrogen migration under the catalysis of acid to form a zwitterionic intermediate II, and then the spirohexenone condensed color mite skeleton is generated through the intramolecular dearomatization-cyclization reaction. The synthetic principle route is specifically as follows:
preferably, the synthesis method as described above is carried out at room temperature.
In the synthesis method described above, the solvent is an alcohol or a halogenated hydrocarbon. Preferably, the solvent is hexafluoroisopropanol or 1, 2-dichloroethane. More preferably, the solvent is 1, 2-dichloroethane. The solvent is used in the following amount: 10 to 20L of solvent is added per mol of the p-methylenequinone derivative.
In the synthesis method, the catalyst is added before the reaction, and the catalyst is Bronsted acid or Lewis acid. Preferably, the catalyst is any one of scandium trifluoromethane sulfonate, diphenyl phosphate or binaphthol phosphate. More preferably, the catalyst is scandium triflate.
In the synthesis method, the catalyst is used in an amount of 5 to 50mol%. Preferably, the catalyst is used in an amount of 10mol%.
Based on the same inventive concept, the present invention also provides a pharmaceutical composition comprising a 3-spirohexenone substituted chroman bioactive scaffold as described above and pharmaceutically acceptable salts, solvates, hydrates, polymorphs, co-crystals, tautomers, geometric isomers, enantiomers, diastereomers or mixtures or prodrugs thereof, and a pharmaceutically acceptable carrier, diluent, excipient or combination thereof. The carrier, diluent, excipient are not particularly limited in the present invention, and may be carriers, diluents, excipients well known to those skilled in the art as suitable for pharmaceutical compositions.
The beneficial effects of the invention are as follows:
1. the invention synthesizes the 3-spirohexenone substituted chroman skeleton with one-step reaction under mild reaction condition, and the technical scheme of the invention provides a convenient and simple synthesis method for the 3-spirohexenone substituted chroman skeleton, thereby realizing the efficient construction of the 3-spirohexenone substituted chroman skeleton through the hydrogen migration process for the first time.
2. The invention develops a method for efficiently synthesizing 3-spirohexenone substituted chroman compounds with multiple functional groups and multiple structures, provides a compound library with multiple structures and 3-spirohexenone substituted chroman skeletons, and provides a new model molecule for drug development.
3. The method has mild reaction conditions and good substrate universality, the substituent of the substrate can be an electron-withdrawing group or an electron-donating group, and the position of the substituent has no obvious influence on the reaction yield. The invention provides experimental basis for the efficient construction of the 3-spirohexenone substituted chroman skeleton with good biological activity, and has good practical significance and application value.
Drawings
FIG. 1 is a synthetic process scheme of the present invention.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used in this specification includes any and all combinations of one or more of the associated listed items.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials, instruments, etc. used in the examples described below are all commercially available unless otherwise specified; the reaction vessel used in the examples below was a 25mL thick-walled pressure-resistant tube.
Example 1
The embodiment provides a synthesis method of a 3-spirohexenone substituted chroman bioactive framework, which comprises the following steps:
taking 0.1mmol of p-methylene quinone derivative in a reaction tube, sequentially adding 1mL of 1, 2-dichloroethane, adding 10mol% of catalyst scandium triflate, continuously stirring at room temperature, and carrying out sample application tracking reaction by a thin layer chromatography plate until the raw materials are completely reacted. After the reaction is completed, separating and purifying by using a silica gel column, and steaming the purified product to obtain a target product with the yield of 94%. The reaction formula is as follows:
example 2
The process of this example was essentially the same as that of example 1, except that the catalyst was nickel trifluoromethane sulfonate, the reaction temperature was 60℃and the yield was 93%.
Example 3
The process of this example was essentially the same as that of example 1, except that the catalyst was copper trifluoromethane sulfonate, the reaction temperature was 80℃and the yield was 94%.
Example 4
The procedure of this example was essentially the same as in example 1, except that the catalyst was trifluoromethanesulfonic acid, the reaction temperature was room temperature and the yield was 12%.
Example 5
The procedure of this example was essentially the same as in example 1, except that the catalyst was p-toluenesulfonic acid, the reaction temperature was room temperature and the yield was 16%.
Example 6
The procedure of this example was the same as in example 1, except that 3mol% scandium trifluoromethane sulfonate was added as a catalyst, and the yield was 79%.
Example 7
The procedure of this example was the same as in example 1, except that scandium trifluoromethane sulfonate was added as a catalyst in an amount of 1mol% and the yield was 37%.
Example 8
The procedure of this example was substantially the same as in example 1, except that 2mL of 1, 2-dichloroethane was added as a solvent, and the yield was 84%.
Example 9
The procedure of this example was substantially the same as in example 1, except that 0.5mL of 1, 2-dichloroethane was added as a solvent, and the yield was 73%.
From the above analysis of parallel test results, it can be seen that: the synthesis reaction of the present invention was carried out under the conditions of example 1, with the highest yield of the target product.
In the following examples 10 to 33, reactions were carried out according to the procedure of example 1; 0.1mmol of a p-methylenequinone derivative was taken in a reaction tube, 1mL of 1, 2-dichloroethane was sequentially added, and 10mol% scandium triflate was added. The reaction temperature of the system is controlled to be room temperature, stirring is continuously carried out, and the reaction is tracked by thin layer chromatography plate sample application until the raw materials are completely reacted. After the reaction is completed, separating and purifying by using a silica gel column, and performing rotary evaporation on the purified products to obtain target products respectively.
Example 10
Raw materials:
the product is: the chemical formula: c (C) 32 H 40 O 2
Molecular weight: 456.3028
Structural formula:
yield: 94%
1 H NMR(300MHz,Chloroform-d)δ7.23(m,6H),7.02(d,J＝6.9Hz,1H),6.93(t,J＝7.5Hz,1H),6.78(d,J＝2.6Hz,1H),6.42(d,J＝2.9Hz,1H),5.10(s,1H),3.40(d,J＝16.2Hz,1H),2.77(d,J＝16.4Hz,1H),1.40(s,9H),1.13(s,9H),1.07(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.8,152.9,149.1,148.3,142.0,138.3,137.9,136.7,128.4,127.9,127.5,127.2,125.1,121.0,119.6,84.2,41.5,37.8,35.1,35.0,34.8,29.9,29.3,29.1.HRMS(ESI)m/z:[M+H] + Calcd for C 32 H 41 O 2 + 457.3101；found:457.3113.
Example 11
Raw materials:
the product is: the chemical formula: c (C) 33 H 42 O 2
Molecular weight: 470.3185
Structural formula:
yield: 92 percent of
1 H NMR(300MHz,Chloroform-d)δ7.31–7.13(m,5H),7.04(d,J＝2.2Hz,1H),6.82(s,1H),6.79(d,J＝2.9Hz,1H),6.42(d,J＝2.9Hz,1H),5.07(s,1H),3.35(d,J＝16.5Hz,1H),2.72(d,J＝16.5Hz,1H),2.32(s,3H),1.40(s,9H),1.13(s,9H),1.08(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.9,150.7,149.0,148.2,142.1,138.1,136.9,129.9,128.3,128.0,127.5,127.2,126.0,119.3,84.2,41.6,37.8,35.1,34.8,34.8,30.0,29.3,29.2,21.1.HRMS(ESI)m/z:[M+H] + Calcd for C 33 H 43 O 2 + 471.3258；found:471.3269.
Example 12
Raw materials:
the product is: the chemical formula: c (C) 36 H 48 O 2
Molecular weight: 512.3654
Structural formula:
yield: 93%
1 H NMR(300MHz,Chloroform-d)δ7.28–7.25(m,1H),7.22(dd,J＝6.4,3.4Hz,5H),6.99(d,J＝2.2Hz,1H),6.81(d,J＝2.8Hz,1H),6.48–6.35(m,1H),5.07(s,1H),3.39(d,J＝16.5Hz,1H),2.75(d,J＝16.5Hz,1H),1.41(s,9H),1.34(s,9H),1.14(s,9H),1.08(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.9,150.6,148.9,148.1,143.3,142.2,138.3,137.5,136.9,128.3,127.5,127.1,124.3,122.4,118.7,84.2,41.8,38.0,35.1,34.8,34.5,31.7,30.0,29.3,29.2.HRMS(ESI)m/z:[M+H] + Calcd for C 36 H 49 O 2 + 513.3727；found:513.3737.
Example 13
Raw materials:
the product is: the chemical formula: c (C) 33 H 42 O 2
Molecular weight: 470.3185
Structural formula:
yield: 93%
1 H NMR(300MHz,Chloroform-d)δ7.24(d,J＝7.8Hz,2H),7.10(dt,J＝25.7,7.7Hz,4H),6.94(t,J＝7.6Hz,1H),6.78(d,J＝2.6Hz,1H),6.43(d,J＝2.7Hz,1H),5.44(s,1H),3.43(d,J＝16.3Hz,1H),2.84(d,J＝16.4Hz,1H),2.36(s,3H),1.36(s,9H),1.18(s,9H),1.03(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.8,153.4,149.3,148.8,140.4,138.4,138.0,134.8,134.5,129.9,128.2,128.0,127.9,125.1,125.1,120.9,119.7,79.9,42.5,38.4,35.2,34.9,34.7,30.4,29.8,29.3,29.1,20.4.HRMS(ESI)m/z:[M+H] + Calcd for C 33 H 43 O 2 + 471.3258；found:471.3268.
Example 14
Raw materials:
the product is: the chemical formula: c (C) 33 H 42 O 2
Molecular weight: 490.3185
Structural formula:
yield: 91%
1 H NMR(300MHz,Chloroform-d)δ7.27–7.21(m,1H),7.12(t,J＝7.4Hz,1H),7.08–6.96(m,4H),6.93(t,J＝7.5Hz,1H),6.77(d,J＝2.9Hz,1H),6.42(d,J＝2.9Hz,1H),5.07(s,1H),3.39(d,J＝16.4Hz,1H),2.76(d,J＝16.5Hz,1H),2.29(s,3H),1.41(s,9H),1.12(s,9H),1.08(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.9,152.9,149.0,148.2,142.1,138.3,138.0,136.4,129.1,128.2,127.9,127.1,125.1,124.6,121.0,119.6,84.3,41.5,37.8,35.1,35.0,34.8,29.9,29.3,29.2,21.6.HRMS(ESI)m/z:[M+H] + Calcd for C 33 H 43 O 2 + 471.3258；found:471.3267.
Example 15
Raw materials:
the product is: the chemical formula: c (C) 33 H 42 O 2
Molecular weight: 470.3185
Structural formula:
yield: 94%
1 H NMR(400MHz,Chloroform-d)δ7.23(d,J＝7.5Hz,1H),7.07(d,J＝8.1Hz,2H),7.04–6.98(m,3H),6.92(t,J＝7.6Hz,1H),6.76(d,J＝2.8Hz,1H),6.41(d,J＝2.8Hz,1H),5.07(s,1H),3.37(d,J＝16.4Hz,1H),2.75(d,J＝16.5Hz,1H),2.29(s,3H),1.39(s,9H),1.13(s,9H),1.06(s,9H). 13 C NMR(101MHz,Chloroform-d)δ185.9,153.0,148.9,148.1,142.2,138.3,138.1,138.0,133.8,127.9,127.9,127.4,125.1,120.9,119.6,84.1,41.5,37.8,35.1,35.0,34.8,29.9,29.3,29.1,21.3.HRMS(ESI)m/z:[M+H] + Calcd for C 33 H 43 O 2 + 471.3258；found:471.3267.
Example 16
Raw materials:
the product is: the chemical formula: c (C) 38 H 44 O 2
Molecular weight: 532.3341
Structural formula:
yield: 94%
1 H NMR(300MHz,Chloroform-d)δ7.56–7.50(m,2H),7.49–7.39(m,4H),7.35(dt,J＝8.5,2.0Hz,1H),7.30–7.23(m,3H),7.04(dd,J＝7.5,1.7Hz,1H),6.95(t,J＝7.6Hz,1H),6.80(d,J＝2.9Hz,1H),6.45(d,J＝3.0Hz,1H),5.16(s,1H),3.42(d,J＝16.4Hz,1H),2.80(d,J＝16.5Hz,1H),1.43(s,9H),1.15(s,9H),1.09(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.8,152.9,149.2,148.4,141.9,141.3,141.0,138.3,137.9,135.8,128.9,128.0,127.9,127.5,127.3,126.0,125.2,121.1,119.6,84.1,41.6,37.8,35.2,35.0,34.9,29.9,29.3,29.2.HRMS(ESI)m/z:[M+H] + Calcd for C 38 H 45 O 2 + 533.3414；found:533.3422.
Example 17
Raw materials:
the product is: the chemical formula: c (C) 32 H 39 ClO 2
Molecular weight: 490.2639
Structural formula:
yield: 92 percent of
1 H NMR(300MHz,Chloroform-d)δ7.36–7.30(m,1H),7.28–7.14(m,4H),7.05(d,J＝6.8Hz,1H),6.95(t,J＝7.6Hz,1H),6.74(d,J＝2.9Hz,1H),6.66(d,J＝2.9Hz,1H),5.72(s,1H),3.50(d,J＝16.5Hz,1H),2.84(d,J＝16.5Hz,1H),1.37(s,9H),1.16(s,9H),1.07(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.7,153.1,149.8,148.7,140.7,138.3,137.1,134.1,132.8,129.5,129.0,128.1,126.0,125.1,121.2,119.7,80.1,42.5,38.1,35.2,34.9,34.8,29.9,29.4,29.1.HRMS(ESI)m/z:[M+H] + Calcd for C 32 H 40 ClO 2 + 491.2711；found:491.2720.
Example 18
Raw materials:
the product is: the chemical formula: c (C) 32 H 39 ClO 2
Molecular weight: 490.2639
Structural formula:
yield: 94%
1 H NMR(300MHz,Chloroform-d)δ7.28–7.21(m,2H),7.21–7.13(m,2H),7.10(dt,J＝7.5,1.6Hz,1H),7.02(dd,J＝7.6,1.8Hz,1H),6.95(t,J＝7.5Hz,1H),6.74(d,J＝2.9Hz,1H),6.41(d,J＝2.9Hz,1H),5.07(s,1H),3.39(d,J＝16.5Hz,1H),2.79(d,J＝16.5Hz,1H),1.40(s,9H),1.13(s,9H),1.10(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.7,152.6,149.6,148.8,141.4,138.7,138.4,137.3,133.1,128.5,128.5,127.9,127.8,125.6,125.3,121.3,119.5,83.5,41.4,37.7,35.2,34.9,34.9,29.9,29.3,29.2.HRMS(ESI)m/z:[M+H] + Calcd for C 32 H 40 ClO 2 + 491.2711；found:491.2719.
Example 19
Raw materials:
the product is: the chemical formula: c (C) 32 H 39 FO 2
Molecular weight: 474.2934
Structural formula:
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yield: 92 percent of
1 H NMR(300MHz,Chloroform-d)δ7.26–7.21(m,1H),7.21–7.14(m,2H),7.01(d,J＝6.6Hz,1H),6.93(td,J＝8.6,8.0,3.1Hz,3H),6.75(d,J＝2.9Hz,1H),6.39(d,J＝3.0Hz,1H),5.09(s,1H),3.38(d,J＝16.5Hz,1H),2.77(d,J＝16.6Hz,1H),1.39(s,9H),1.13(s,9H),1.08(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.7,162.6(d,J＝246.9Hz),152.8,149.4,148.7,141.7,138.3,137.6,132.7(d,J＝3.0Hz),129.1(d,J＝8.2Hz),127.9,125.2,121.2,119.5,114.2(d,J＝21.6Hz),83.5,41.5,37.8,35.2,34.9,34.9,29.9,29.3,29.2.HRMS(ESI)m/z:[M+H] + Calcd for C 32 H 40 FO 2 + 475.3007；found:475.3016.
Example 20
Raw materials:
the product is: the chemical formula: c (C) 32 H 39 BrO 2
Molecular weight: 534.2133
Structural formula:
yield: 92 percent of
1 H NMR(300MHz,Chloroform-d)δ7.41–7.32(m,2H),7.28–7.20(m,1H),7.08(d,J＝8.4Hz,2H),7.01(d,J＝7.3Hz,1H),6.93(t,J＝7.6Hz,1H),6.74(d,J＝2.9Hz,1H),6.39(d,J＝2.9Hz,1H),5.05(s,1H),3.37(d,J＝16.5Hz,1H),2.76(d,J＝16.6Hz,1H),1.38(s,9H),1.12(s,9H),1.09(s,9H). 13 CNMR(75MHz,Chloroform-d)δ185.6,152.6,149.5,148.8,141.5,138.3,137.5,135.9,130.4,129.1,127.9,125.2,122.3,121.2,119.5,83.6,41.3,37.8,35.2,34.9,34.9,29.9,29.3,29.2.HRMS(ESI)m/z:[M+H] + Calcd for C 32 H 40 BrO 2 + 535.2206；found:535.2188.
Example 21
Raw materials:
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the product is: the chemical formula: c (C) 33 H 39 NO 2
Molecular weight: 481.2981
Structural formula:
yield: 92 percent of
1 H NMR(300MHz,Chloroform-d)δ7.58–7.52(m,1H),7.52–7.43(m,2H),7.37(td,J＝7.6,1.8Hz,1H),7.27–7.21(m,1H),7.10–7.01(m,1H),6.97(t,J＝7.6Hz,1H),6.72(d,J＝0.8Hz,2H),5.62(s,1H),3.54(d,J＝16.6Hz,1H),2.88(d,J＝16.5Hz,1H),1.36(s,9H),1.13(s,9H),1.09(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.6,152.5,150.2,149.8,140.4,140.1,138.3,136.5,132.0,131.8,128.9,128.7,128.1,125.3,121.6,119.5,118.1,112.1,81.4,42.4,37.8,35.2,35.0,34.9,29.9,29.4,29.1.HRMS(ESI)m/z:[M+H] + Calcd for C 33 H 40 NO 2 + 482.3054；found:482.3065.
Example 22
Raw materials:
the product is: the chemical formula: c (C) 32 H 39 NO 4
Molecular weight: 501.2879
Structural formula:
yield: 94%
1 H NMR(300MHz,Chloroform-d)δ8.13(dt,J＝10.1,1.6Hz,2H),7.57(dt,J＝7.7,1.4Hz,1H),7.43(t,J＝7.9Hz,1H),7.26(dd,J＝7.6,1.9Hz,1H),7.04(dd,J＝7.5,1.9Hz,1H),6.97(t,J＝7.5Hz,1H),6.76(d,J＝2.9Hz,1H),6.46(d,J＝2.9Hz,1H),5.21(s,1H),3.43(d,J＝16.7Hz,1H),2.83(d,J＝16.6Hz,1H),1.40(s,9H),1.08(s,9H),1.06(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.5,152.3,150.2,149.6,147.2,140.9,138.7,138.4,136.7,133.3,128.2,128.0,125.4,123.4,122.6,121.6,119.3,83.0,41.4,37.5,35.2,34.9,30.0,29.3,29.2.HRMS(ESI)m/z:[M+H] + Calcd for C 32 H 40 NO 4 + 502.2952；found:502.2962.
Example 23
Raw materials:
the product is: the chemical formula: c (C) 33 H 39 F 3 O 2
Molecular weight: 524.2902
Structural formula:
yield: 85%
1 H NMR(300MHz,Chloroform-d)δ7.51(d,J＝8.2Hz,2H),7.34(d,J＝8.1Hz,2H),7.29–7.21(m,1H),7.07–6.90(m,2H),6.76(d,J＝2.9Hz,1H),6.42(d,J＝2.9Hz,1H),5.15(s,1H),3.41(d,J＝16.6Hz,1H),2.80(d,J＝16.6Hz,1H),1.40(s,9H),1.12(s,9H),1.07(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.5,152.5,149.6,149.0,141.2,140.7,138.4,137.2,130.7(q,J＝32.6Hz),128.0,127.9,125.3,124.2(q,J＝3.9Hz),124.1(q,J＝270.7Hz),121.4,119.5,83.6,41.4,37.8,35.2,35.0,34.9,29.9,29.3,29.1.HRMS(ESI)m/z:[M+H] + Calcd for C 33 H 40 F 3 O 2 + 525.2975；found:525.2983.
Example 24
Raw materials:
the product is: the chemical formula: c (C) 34 H 42 O 4
Molecular weight: 514.3083
Structural formula:
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yield: 91%
1 H NMR(300MHz,Chloroform-d)δ7.96–7.89(m,2H),7.28(d,J＝8.4Hz,2H),7.25(d,J＝8.7Hz,1H),7.05–6.98(m,1H),6.94(t,J＝7.5Hz,1H),6.77(d,J＝2.9Hz,1H),6.43(d,J＝2.9Hz,1H),5.14(s,1H),3.89(s,3H),3.40(d,J＝16.5Hz,1H),2.78(d,J＝16.5Hz,1H),1.38(s,9H),1.11(s,9H),1.07(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.6,166.8,152.6,149.4,148.8,141.7,141.4,138.4,137.4,130.1,128.6,127.9,127.6,125.3,121.3,119.5,83.8,52.2,41.3,37.8,35.2,34.9,34.9,29.9,29.3,29.2.HRMS(ESI)m/z:[M+H] + Calcd for C 34 H 43 O 4 + 515.3156；found:515.3167.
Example 25
Raw materials:
the product is: the chemical formula: c (C) 33 H 42 O 4 S
Molecular weight: 534.2804
Structural formula:
yield: 83%
1 H NMR(300MHz,Chloroform-d)δ7.82(d,J＝8.0Hz,2H),7.40(d,J＝8.1Hz,2H),7.25(d,J＝6.8Hz,1H),7.03(d,J＝7.0Hz,1H),7.00–6.91(m,1H),6.70(d,J＝2.3Hz,1H),6.40(d,J＝2.2Hz,1H),5.18(s,1H),3.42(d,J＝16.6Hz,1H),2.94(s,3H),2.85(d,J＝16.7Hz,1H),1.38(s,9H),1.09(s,9H),1.06(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.6,152.3,149.9,149.3,142.5,141.0,140.4,138.4,136.9,128.7,128.0,126.3,125.4,121.6,119.3,83.3,44.8,41.4,37.5,35.2,34.9,29.9,29.3,29.1.HRMS(ESI)m/z:[M+H] + Calcd for C 34 H 43 O 4 S + 535.2877；found:535.2873.
Example 26
Raw materials:
the product is: the chemical formula: c (C) 36 H 42 O 2
Molecular weight: 506.3185
Structural formula:
yield: 94%
1 H NMR(300MHz,Chloroform-d)δ7.99(d,J＝8.2Hz,1H),7.88–7.79(m,1H),7.75(d,J＝8.1Hz,1H),7.56–7.45(m,2H),7.44(ddd,J＝7.9,6.8,1.2Hz,2H),7.38(t,J＝7.7Hz,1H),7.27(d,J＝6.4Hz,1H),7.10(dd,J＝7.6,1.8Hz,1H),6.98(t,J＝7.6Hz,1H),6.79(d,J＝2.9Hz,1H),6.40(d,J＝2.9Hz,1H),6.13(s,1H),3.57(d,J＝16.5Hz,1H),2.94(d,J＝16.5Hz,1H),1.40(s,10H),1.15(s,9H),0.60(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.4,153.6,149.6,148.0,141.9,138.5,137.6,133.3,132.1,131.0,129.5,128.8,128.1,126.3,126.1,125.3,125.1,124.6,122.8,121.1,119.9,79.3,42.6,38.3,35.1,35.0,34.3,29.9,29.4,28.5.HRMS(ESI)m/z:[M+H] + Calcd for C 36 H 43 O 2 + 507.3258；found:507.3267.
Example 27
Raw materials:
the product is: the chemical formula: c (C) 36 H 42 O 2
Molecular weight: 506.3185
Structural formula:
yield: 95% of
1 H NMR(300MHz,Chloroform-d)δ7.82–7.73(m,2H),7.73–7.64(m,2H),7.50–7.41(m,2H),7.34(dd,J＝8.4,1.4Hz,1H),7.27(d,J＝7.5Hz,1H),7.05(d,J＝7.2Hz,1H),6.96(t,J＝7.6Hz,1H),6.87(d,J＝2.8Hz,1H),6.51(d,J＝2.9Hz,1H),5.28(s,1H),3.45(d,J＝16.3Hz,1H),2.81(d,J＝16.5Hz,1H),1.42(s,9H),1.11(s,9H),0.98(s,9H). 13 C NMR(75MHz,Chloroform-d)δ185.8,153.0,149.1,148.4,141.9,138.4,138.0,134.5,133.3,132.3,128.0,128.0,127.8,126.8,126.7,126.2,126.2,125.4,125.2,121.1,119.7,84.4,41.7,37.9,35.1,35.0,34.8,29.9,29.3,29.1.HRMS(ESI)m/z:[M+H] + Calcd for C 36 H 43 O 2 + 507.3258；found:507.3267.
Example 28
Raw materials:
the product is: the chemical formula: c (C) 28 H 38 O 2
Molecular weight: 406.2872
Structural formula:
yield: 92 percent of
1 H NMR(300MHz,Chloroform-d)δ7.20(dd,J＝7.5,1.9Hz,1H),6.98–6.83(m,2H),6.62(d,J＝2.9Hz,1H),6.39(d,J＝2.9Hz,1H),5.67(ddd,J＝16.9,10.6,6.2Hz,1H),5.36(dt,J＝17.2,1.4Hz,1H),5.22(dt,J＝10.6,1.3Hz,1H),4.49(d,J＝6.2Hz,1H),3.18(d,J＝16.4Hz,1H),2.67(d,J＝16.4Hz,1H),1.41(s,9H),1.25(s,9H),1.17(s,9H). 13 C NMR(75MHz,Chloroform-d)δ186.7,152.1,149.3,149.0,141.9,138.9,138.1,133.1,127.8,125.2,120.8,119.5,118.7,81.6,40.1,37.1,35.2,35.1,34.9,29.8,29.7,29.6.HRMS(ESI)m/z:[M+H] + Calcd for C 28 H 39 O 2 + 407.2945；found:407.2952.
Example 29
Raw materials:
the product is: the chemical formula: c (C) 30 H 36 O 2
Molecular weight: 428.2715
Structural formula:
yield: 92 percent of
1 H NMR(400MHz,Chloroform-d)δ7.25(d,J＝8.0Hz,1H),7.21(s,5H),7.01(d,J＝7.3Hz,1H),6.94(t,J＝7.6Hz,1H),6.83–6.78(m,1H),6.47–6.42(m,1H),5.13(s,1H),3.41(d,J＝16.5Hz,1H),2.87(dp,J＝28.3,6.9Hz,2H),2.72(d,J＝16.5Hz,1H),1.40(s,9H),1.02(d,J＝7.0Hz,3H),0.99(d,J＝7.0Hz,3H),0.96(d,J＝6.9Hz,3H),0.83(d,J＝6.9Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ184.8,152.8,147.0,146.2,142.4,138.5,138.3,136.8,128.4,127.8,127.3,127.3,125.2,121.0,119.5,83.9,41.8,37.7,35.0,29.9,26.8,26.3,22.8,22.0,21.7,21.6.HRMS(ESI)m/z:[M+H] + Calcd for C 30 H 37 O 2 + 429.2788；found:429.2797.
Example 30
Raw materials:
the product is: the chemical formula: c (C) 54 H 72 O 4
Molecular weight: 784.5431
Structural formula:
yield: 80 percent of
1 H NMR(400MHz,Chloroform-d)δ7.17(dd,J＝7.1,3.6Hz,2H),6.87(dq,J＝14.2,7.5Hz,4H),6.55(d,J＝9.1Hz,2H),6.41(d,J＝32.9Hz,2H),5.78(d,J＝30.3Hz,2H),4.48(s,2H),2.95(d,J＝16.3Hz,2H),2.65(d,J＝15.7Hz,2H),1.37(s,18H),1.20(s,18H),1.16(s,18H). 13 C NMR(101MHz,Chloroform-d)δ186.3,151.4,149.5,148.5,141.7,139.5,137.8,130.2,127.8,125.1,120.8,119.3,80.2,39.9,36.4,35.2,35.0,34.9,29.8,29.6,29.5.HRMS(ESI)m/z:[M+H] + Calcd for C 54 H 73 O 4 + 785.5503；found:785.5500.
Example 31
Raw materials:
the product is: the chemical formula: c (C) 62 H 88 O 4
Molecular weight: 896.6683
Structural formula:
yield: 78%
1 H NMR(400MHz,Chloroform-d)δ7.16(d,J＝1.8Hz,2H),6.86–6.82(m,2H),6.57(d,J＝2.5Hz,2H),6.45(d,J＝2.6Hz,2H),5.86–5.74(m,2H),4.47–4.42(m,2H),2.95(d,J＝16.4Hz,2H),2.58(d,J＝16.4Hz,2H),1.34(s,18H),1.28(s,18H),1.20(s,18H),1.18(s,18H). 13 C NMR(101MHz,Chloroform-d)δ186.5,149.3,149.1,148.3,143.0,142.1,139.9,137.0,130.1,124.1,122.3,118.5,80.0,40.2,36.8,35.2,35.0,35.0,34.4,31.7,29.9,29.7,29.6.HRMS(ESI)m/z:[M+H] + Calcd for C 62 H 89 O 4 + 897.6755；found:897.6762.
Example 32
Raw materials:
the product is: the chemical formula: c (C) 58 H 74 O 4
Molecular weight: 834.5587
Structural formula:
yield: 87% of
1 H NMR(400MHz,Chloroform-d)δ7.21(d,J＝7.6Hz,2H),7.06(d,J＝2.0Hz,2H),6.99(d,J＝8.3Hz,4H),6.91(t,J＝7.6Hz,2H),6.77(d,J＝2.5Hz,2H),6.36(d,J＝2.5Hz,2H),5.02(s,2H),3.36(d,J＝16.5Hz,2H),2.77(d,J＝16.6Hz,2H),1.30(s,18H),1.14(s,18H),1.01(s,18H). 13 C NMR(101MHz,Chloroform-d)δ185.5,152.9,148.9,148.2,141.8,138.5,137.9,136.6,127.8,126.3,125.1,121.0,119.5,83.8,41.5,37.5,35.2,34.9,34.8,30.4,29.8,29.6,29.4,29.3,29.2,29.0.HRMS(ESI)m/z:[M+H] + Calcd for C 58 H 75 O 4 + 835.5660；found:835.5669.
Example 33
Raw materials:
the product is: the chemical formula: c (C) 66 H 90 O 4
Molecular weight: 946.6839
Structural formula:
yield: 82%
1 H NMR(400MHz,Chloroform-d)δ7.24–7.20(m,2H),7.04(s,4H),6.95(s,2H),6.77(d,J＝2.5Hz,2H),6.39(d,J＝2.5Hz,2H),5.00(s,2H),3.35(d,J＝16.5Hz,2H),2.73(d,J＝16.6Hz,2H),1.32(s,18H),1.32(s,18H),1.09(s,18H),1.08(s,18H). 13 C NMR(101MHz,Chloroform-d)δ185.7,150.5,148.7,148.1,143.2,142.3,138.3,136.7,126.1,124.2,122.3,118.6,83.8,41.8,37.7,35.1,35.1,34.8,34.4,31.7,29.9,29.4,29.2.HRMS(ESI)m/z:[M+H] + Calcd for C 66 H 91 O 4 + 947.6912；found:947.6918.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
- The 1, 3-spirohexenone is substituted for chroman bioactive frameworks, and is characterized by having the following structural formula:
wherein R is 1 Is any one of hydrogen atom, methyl and tertiary butyl; r is R 2 Is any one of alkenyl and aryl; r is R 3 Is either isopropyl or tert-butyl. - 2. The method for synthesizing the 3-spirohexenone-substituted chroman bioactive framework according to claim 1, comprising the following steps:uniformly mixing a p-methylene quinone derivative and a catalyst in a solvent, and stirring and reacting at rt-100 ℃ to prepare a 3-spirohexenone substituted chroman compound;wherein the structural formula of the p-methylenequinone derivative is shown as follows:
wherein R is 1 Is any one of hydrogen atom, methyl and tertiary butyl; r is R 2 Is any one of alkenyl and aryl; r is R 3 Is either isopropyl or tert-butyl. - 3. The synthetic method according to claim 2, characterized in that the solvent is 1, 2-dichloroethane or hexafluoroisopropanol.
- 4. The method of synthesis according to claim 2, wherein the solvent is used in an amount of: 10 to 20L of solvent is added per mol of the p-methylenequinone derivative.
- 5. The synthetic method of claim 2 wherein the catalyst is added prior to the reaction, the catalyst being a bronsted or lewis acid.
- 6. The method of synthesis according to claim 2 or 5, wherein the catalyst is used in an amount of 5 to 50mol%.
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Non-Patent Citations (2)
| Title |
|---|
| CAIQI ZHUO 等: "Silver(I)-catalyzed novel ipso-cycloaddition and retro-Friedel–Crafts reaction of orthohydroxyphenyl- substituted para-quinone methides", ORG. CHEM. FRONT., vol. 8, pages 6400 - 6404 * |
| XINTONG LV 等: "Aromatization-Driven Cascade [1, 5]-Hydride Transfer/ Spirocyclization Promoted by Fluorinated Alcohols", J. ORG. CHEM., vol. 84, pages 1833 - 1844 * |
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