CN106588854A - Synthetic method of marine natural product Puupehenol - Google Patents
Synthetic method of marine natural product Puupehenol Download PDFInfo
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- CN106588854A CN106588854A CN201611096102.3A CN201611096102A CN106588854A CN 106588854 A CN106588854 A CN 106588854A CN 201611096102 A CN201611096102 A CN 201611096102A CN 106588854 A CN106588854 A CN 106588854A
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- puupehenol
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention relates to a synthetic method of a marine natural product Puupehenol, and belongs to the field of chemical synthesis. The synthetic method comprises the steps: taking (+) aromatic perillaldehyde and hydroxyquinol as starting raw materials, firstly, utilizing (+) aromatic perillaldehyde and p-toluenesulfonhydrazide to form (+) aromatic perillasulfonyl hydrazone, then carrying out palladium-catalyzed cascade Carving migration insertion and intramolecular cyclization reaction of iodine substituted 1,2,4-trimethoxybenzene and (+) aromatic perillasulfonyl hydrazone in an alkali environment to obtain a marine natural product Puupehenol skeleton; and then carrying out hydroxy reduction and double-bond isomerization of a bicyclic sesquiterpanes part of the Puupehenol skeleton, and carrying out oxidation, reduction, cyclization and protection group removal to obtain the final target product Puupehenol. The synthetic method has the advantages of fewer reaction steps, simple operation, and good product selectivity, and is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of synthetic method of marine natural products Puupehenol.
Background technology
Marine natural products Puupehenol belongs to Puupehenone class marine natural products.Marine natural products
Puupehenone is in 1979 first from deep-sea spongeHeteronemaWithHyrtioseubnammaIn first separation and Extraction obtain
To (Pure and Applied Chemistry, 1979, 51(9): 1893-1900).Subsequently in 1986,
ShigeoKohmoto et al. is from deep-sea spongeStrongylophoraihartmaniIn again separation and Extraction obtain, and by matter
The technologies such as spectrum, infrared and nuclear magnetic resonance are identified its structure, it is found that it is a kind of cytotoxic sequiterpene
Class-methylenation quinone (The Journal of Organic Chemistry, 1993, 58(24):6565-6569), tie
Structure such as Fig. 1.Its derivative is that important ocean metabolin is presented including cytotoxicity, antiviral, anticancer, antimycotic, anti-
The multiple biological activities such as malaria, treating tuberculosis and immunological regulation (Tetrahedron, 2000, 56(7): 949–953; The Journal of Organic Chemistry, 1995, 60(22): 7290-7292; Journal of natural products, 1998, 61(12): 1502–1508).Synthetic method report at present for Puupehenol is less, and greatly
Part all has methyl C-8 in longer synthetic route, initiation material or reaction reagent costliness, course of reaction and selects phase for three-dimensional
Difference, the low drawback of yield.As Alejandro F. Barrero et al. were reported in the research of 1997, the reaction of the steps of Jing 8 is completed
Puupehenol study on the synthesis (Tetrahedron, 1999, 55,(52):15181-15208), but the method yield
Extremely low, stereoselectivity is poor, is not appropriate for industrialized production.In view of above-mentioned discussion, exploitation it is a kind of it is easy to operate, with low cost,
The chemical synthesis process of the marine natural products Puupehenol of suitable industrialized production just seems particularly necessary.Present invention report
The natural products synthetic method possess few, easy to operate reactions steps, good product selectivity, be adapted to industrialized production
The advantages of.
The content of the invention
Present invention aim at providing a kind of synthetic method of marine natural products Puupehenol.Reactions steps are few, product
Thing is selectively good, be adapted to industrialized production.
For achieving the above object, the present invention is comprised the following steps：
A) 1,2,4- trimethoxy-benzene 2 is passed through and NIS iodide reactions, synthesizes the trimethoxy-benzene 3 of iodo 1,2,4-；
b)（+）Fragrant perillaldehyde 4 and tolysulfonyl hydrazine reaction, generate（+）Fragrant purple perilla sulphonyl hydrazone 5；
C) He of iodo 1,2,4- trimethoxy-benzenes 3（+）In the basic conditions, via palladium-catalyzed series connection Cabbeen is moved fragrant purple perilla sulphonyl hydrazone 5
Insertion, intramolecular cyclization reaction are moved, synthesizes the basic framework 6 of Puupehenol；
D) in the presence of hydrogen donor and acid, hydroxyl is reduced the basic framework 6 of Puupehenol, while completing the migration of double bond
Reaction, builds alkene terpenoid 7；
E) alkene terpenoid 7 is again through oxidation, reduction process, synthesis alkene terpene diphenol compound 8；
F) the Jing acid catalysis cyclizations of alkene terpene diphenol compound 8, demethylation protection group obtain final goal product Puupehenol 1.
2. step a prioritization scheme described in：The iodide reaction of 1,2,4- trimethoxy-benzene and NIS, prioritizing selection acetonitrile, four
Hydrogen furans etc. is solvent, and reaction temperature is 0ºTo backflow, the reaction time is 1-12 hour condition to C.
3. step b prioritization scheme described in：（+）Fragrant perillaldehyde 4 is generated with unifor（+）Fragrant purple perilla sulphonyl hydrazone 5
The fatty alcohols such as reaction, prioritizing selection methyl alcohol, ethanol are solvent, and reaction temperature is 0ºTo backflow, the reaction time is 1-12 hour to C
Condition.
4. step c prioritization scheme described in：The He of iodo 1,2,4- trimethoxy-benzenes 3（+）Fragrant purple perilla sulphonyl hydrazone 5 is in alkalescence condition
Lower palladium chtalyst is concatenated Cabbeen migration insertion, intramolecular cyclization reaction, prioritizing selection potassium hydroxide, sodium carbonate, cesium carbonate, carbonic acid
Potassium etc. be alkali, bi triphenyl phosphorus palladium chloride, double acetonitrile palladium chlorides, three（Dibenzalacetone）Two palladiums, the [double (diphenyl of 1,1'-
Phosphorus) ferrocene] palladium chloride, tetra-triphenylphosphine palladium etc. be catalyst, prioritizing selection tetrahydrofuran, toluene, acetonitrile, 1,2- dichloros
Ethane, Isosorbide-5-Nitrae-dioxane, DMF etc. are solvent, and reaction temperature is 0ºC to backflow, the reaction time be 6-
24 hours conditions.
5. step d prioritization scheme described in：The basic framework 6 of Puupehenol hydrogen donor and acid in the presence of, hydroxyl quilt
Reduction, while completing the migration of double bond, builds the reaction of alkene terpenoid 7, prioritizing selection trimethyl silane, triethyl group silicon
Alkane, tri-phenyl-silane are hydrogen donor, and trifluoroacetic acid is acid, and dichloromethane is solvent, and reaction temperature is -20ºC to 40ºC, reaction
Time is 3-12 hours conditions.
6. the step e prioritization scheme：Alkene terpenoid 7 is through aoxidizing, the reaction of reduction synthesis phenolic compound 8,
Prioritizing selection DDQ, ammonium ceric nitrate, iodobenzene diacetate etc. are oxidant, and acetone-water, acetonitrile-water, water etc. are anti-
Answer solvent；Prioritizing selection sodium dithionite is reducing agent, and tetrahydrofuran-water etc. is reaction dissolvent, and reaction temperature is room temperature to 0ºC to 40ºC, 1-6 hour reaction time condition.
7. step f prioritization scheme described in：The Jing acid catalysis cyclizations of alkene terpene diphenol compound 8, demethylation protection group are obtained most
The reaction of whole target product Puupehenol1, the prioritizing selection concentrated sulfuric acid, p-methyl benzenesulfonic acid, BFEE etc. are acid, nitro
Propane, toluene, dichloromethane etc. are cyclized for solvent；The deprotections such as prioritizing selection Boron tribromide, alchlor, boron chloride
Base, dichloromethane, toluene etc. are reaction dissolvent, and reaction temperature is -78ºC is to room temperature, 1-6 hour reaction time condition.
Compared with related synthesis report before, the invention has the characteristics that：
1. the present invention with known 1,2,4- trimethoxy-benzenes and（+）Fragrant perillaldehyde is initiation material, few with reactions steps,
Suitable industrialized production；
2. total recovery is high, good product selectivity.
Description of the drawings
Fig. 1 is the concrete synthetic route chart of the present invention.
Specific embodiment
Embodiment 1：Iodo 1,2,4- trimethoxy-benzenes（3, see Fig. 1）Synthesis
Take 1.68 grams of 1,2,4- trimethoxy-benzenes（2,10.0mmol）In being dissolved in 25 milliliters of anhydrous acetonitriles, NIS is added
（10.0mmol）, stirring reaction 2 hours under room temperature, TLC detection reaction terminate.Add 30 milliliters of water, ethyl acetate extraction（30
mL x 3）, merging organic phase, saturated common salt water washing, anhydrous sodium sulfate drying is filtered, concentration, and column chromatography purification obtains white
Solid iodine 2.90 grams of 1,2,4- trimethoxy-benzene of generation, yield is 99%.
Embodiment 2：（+）Fragrant purple perilla hydrazone（5, see Fig. 1）Synthesis
Take（+）2.38 grams of fragrant perillaldehyde（4,10.0 mmol）In being dissolved in 30 milliliters of absolute methanols, unifor 1.86 is added
Gram（10.0 mmol）, stirring reaction 3 hours under room temperature, TLC detection reaction terminate.Concentration, obtains final product white solid（+）Fragrant purple perilla
Sulphonyl hydrazone.
Embodiment 3：The basic framework of Puupehenol（6, see Fig. 1）Synthesis
Take（+）Fragrant 407 milligrams of purple perilla sulphonyl hydrazone（5,1.0mmol）In being dissolved in 4 milliliters of anhydrous tetrahydro furans, four triphenylphosphines are added
23 milligrams of palladium（0.02 mmol）, 622 milligrams of potassium carbonate（4.5 mmol）Row's argon gas three times is filled repeatedly, drains air.Separately take iodo
294 milligrams of 1,2,4- trimethoxy-benzenes（3, see Fig. 1）In being dissolved in 2 milliliters of anhydrous tetrahydro furans, it is slowly added dropwise to above-mentioned reactant
In system, 110 are warming up tooC, stirring reaction 10 hours, TLC detection reactions terminate.30 milliliters of water, acetic acid are added in reaction system
Ethyl ester is extracted（10 mL x 3）, merging organic phase, saturated common salt water washing, anhydrous sodium sulfate drying is filtered, concentration, column chromatography
Purification, obtains 315 milligrams of pale yellow oil, and yield is 81%.
Embodiment 4：Alkene terpenoid（7, see Fig. 1）Synthesis
Take 194 milligrams of the basic framework of Puupehenol（6,0.5 mmol）In being dissolved in 2 milliliters of dry methylene chlorides, three second are added
174 milligrams of base silane（1.5 mmol）0oC stirring reactions 5 minutes, are added dropwise 114 milligrams of trifluoroacetic acid（1.0 mmol）Continue to react
5 hours, TLC detection reactions terminated.Add 10 milliliters of water, ethyl acetate extraction（10 mL x 3）, merge organic phase, saturation food
Salt water washing, anhydrous sodium sulfate drying is filtered, concentration, column chromatography purification, obtains 159 milligrams of faint yellow solid, and yield is 85%.
Embodiment 5：Alkene terpene diphenol compound（8, see Fig. 1）Synthesis
Take 186 milligrams of alkene terpenoid（7,0.5 mmol）It is dissolved in 2 milliliters of acetonitrile-waters（1:1）In, add ammonium ceric nitrate 822
Milligram（1.5 mmol）Reaction 2 hours is stirred at room temperature, TLC detection reactions terminate.Add 10 milliliters of water, ethyl acetate extraction（10
mL x 3）, merging organic phase, saturated common salt water washing, anhydrous sodium sulfate drying is filtered, concentration, and column chromatography purification obtains yellow
159 milligrams of solid, yield is 93%.By 171 milligrams of yellow solid（0.5 mmol）It is dissolved in 2 milliliters of tetrahydrofuran-water（1：1）In,
Add 237 milligrams of sodium dithionite（1.5 mmol）, 32.2 milligrams of TBAB（0.1 mmol）Reaction 2 is stirred at room temperature
Hour, TLC detection reactions terminate.Add 10 milliliters of water, ethyl acetate extraction（10 mL x 3）, merge organic phase, saturated common salt
Water washing, anhydrous sodium sulfate drying is filtered, and concentration is obtained final product.
Embodiment 6：Puupehenol（1, see Fig. 1）Synthesis
By 177 milligrams of alkene terpene diphenol compound（8,0.5mmol）In being dissolved in 2 milliliters of dry methylene chlorides, row's argon gas is filled repeatedly
Three times, air is drained, add 355 milligrams of BFEE（2.5 mmol）, reaction 2 hours, TLC detection reactions is stirred at room temperature
Terminate.Water quenching is added to go out reaction, ethyl acetate is extracted（10 mL x 3）, merge organic phase, saturated common salt water washing, anhydrous sulphur
Sour sodium is dried, and filters, concentration, column chromatography purification, obtains pale yellow oil.Take 34 milligrams of grease of gained（0.1 mmol）It is dissolved in
In 2 milliliters of dry methylene chlorides, row's argon gas three times is filled repeatedly, drain air, be cooled to -78oC.Add boron chloride（1 M
in DCM）0.3 milliliter（0.3 mmol）, after be warming up to 0oC stirring reactions 1.5 hours, TLC detection reactions terminate.Add water quenching
Go out reaction, dichloromethane extraction（10 mL x 3）, merging organic phase, saturated common salt water washing, anhydrous sodium sulfate drying is filtered,
Concentration, column chromatography purification, obtains 150 milligrams of pale yellow oil, and yield is 91%.
The present invention relates to the iodide reaction of 1,2,4- trimethoxy-benzenes,（+）Fragrant perillaldehyde is generated（+）Fragrant purple perilla sulphonyl hydrazone
Reaction, palladium chtalyst series connection Cabbeen migration insertion with intramolecular cyclization reaction, acid catalyzed hydroxyl reduction with double-bond isomerism reaction,
The 6 steps reactions such as redox reaction, the cyclisation of acid effect and Deprotection, synthesize marine natural products Puupehenol.It is above-mentioned
It is only the preferred embodiments of the present invention to be embodied as illustrating, and is not the restriction for making other forms to the present invention.
Claims (7)
1. a kind of synthetic method of marine natural products Puupehenol, it is characterised in that according to shown in accompanying drawing, including following conjunction
Into step：
A) 1,2,4- trimethoxy-benzene 2 is passed through and NIS iodide reactions, synthesizes the trimethoxy-benzene 3 of iodo 1,2,4-；
B) fragrant perillaldehyde 4 and tolysulfonyl hydrazine reaction, generate fragrant purple perilla sulphonyl hydrazone 5；
C) in the basic conditions, via palladium-catalyzed series connection Cabbeen migration is inserted for iodo 1,2,4- trimethoxy-benzenes 3 and fragrant purple perilla sulphonyl hydrazone 5
Enter, intramolecular cyclization reaction, synthesize Puupehenol basic framework 6；
D) in the presence of hydrogen donor and acid, hydroxyl is reduced the basic framework 6 of Puupehenol, while completing the migration of double bond
Reaction, builds alkene terpenoid 7；
E) alkene terpenoid 7 is again through oxidation, reduction process, synthesis alkene terpene diphenol compound 8；
F) the Jing acid catalysis cyclizations of alkene terpene diphenol compound compound 8, demethylation protection group obtain final goal product
Puupehenol 1。
2. according to claim 11, the iodide reaction of 2,4- trimethoxy-benzenes and NIS, prioritizing selection acetonitrile, tetrahydrochysene furan
Mutter etc. as solvent, reaction temperature is 0ºTo backflow, the reaction time is 1-12 hour condition to C.
3. fragrant perillaldehyde 4 according to claim 1 and unifor generate the reaction of fragrant purple perilla sulphonyl hydrazone 5, preferentially
The fatty alcohols such as methyl alcohol, ethanol are selected to be solvent, reaction temperature is 0ºTo backflow, the reaction time is 1-12 hour condition to C.
4. in the basic conditions palladium is urged for iodo 1,2,4- trimethoxy-benzenes 3 according to claim 1 and fragrant purple perilla sulphonyl hydrazone 5
Change is concatenated Cabbeen migration insertion, intramolecular cyclization reaction, prioritizing selection potassium hydroxide, sodium carbonate, cesium carbonate, potassium carbonate etc.
Alkali, bi triphenyl phosphorus palladium chloride, double acetonitrile palladium chlorides, three（Dibenzalacetone）Two palladiums, [double (diphenylphosphines) two of 1,1'-
Luxuriant iron] palladium chloride, tetra-triphenylphosphine palladium etc. be catalyst, prioritizing selection tetrahydrofuran, toluene, acetonitrile, 1,2- dichloroethanes,
Isosorbide-5-Nitrae-dioxane, DMF etc. are solvent, and reaction temperature is 0ºTo backflow, the reaction time is 6-24 hours to C
Condition.
5. the basic framework 6 of Puupehenol according to claim 1 in the presence of hydrogen donor and acid, gone back by hydroxyl
Original, while completing the migration of double bond, builds the reaction of Puupehenol skeletons 7, prioritizing selection trimethyl silane, triethyl group silicon
Alkane, tri-phenyl-silane, 2,6- dimethyl-Isosorbide-5-Nitrae-dihydro -3,5- pyridinedicarboxylic acid diethylesters etc. are hydrogen donor, and trifluoroacetic acid is
Acid, dichloromethane is solvent, and reaction temperature is -20ºC to 40ºC, the reaction time is 3-12 hours conditions.
6. alkene terpenoid 7 according to claim 1 passes through oxidation, the reaction of reduction synthesis phenolic compound 8, preferentially
Select DDQ, ammonium ceric nitrate, iodobenzene diacetate etc. for oxidant, acetone-water, acetonitrile-water, water etc. are molten for reaction
Agent；Prioritizing selection sodium dithionite is reducing agent, and tetrahydrofuran-water etc. is reaction dissolvent, and reaction temperature is room temperature to 0ºC
To 40ºC, 1-6 hour reaction time condition.
7. the Jing acid catalysis cyclizations of alkene terpene diphenol compound according to claim 18, demethylation protection group obtain final mesh
The acid such as the reaction of mark product Puupehenol 1, the prioritizing selection concentrated sulfuric acid, p-methyl benzenesulfonic acid, BFEE, nitropropane,
Toluene, dichloromethane etc. are cyclized for solvent；The Deprotections such as prioritizing selection Boron tribromide, alchlor, boron chloride, two
Chloromethanes, toluene etc. are reaction dissolvent, and reaction temperature is -78ºC is to room temperature, 1-6 hour reaction time condition.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107266410A (en) * | 2017-07-29 | 2017-10-20 | 哈尔滨工业大学（威海） | A kind of 8 epi puupehedione synthetic method |
| CN109096114A (en) * | 2018-10-09 | 2018-12-28 | 哈尔滨工业大学（威海） | A kind of synthetic method of marine natural products smenodiol |
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2016
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| CN102838579A (en) * | 2011-06-20 | 2012-12-26 | 昆明制药集团股份有限公司 | Method for preparing 1,3,6,7-tetrahydroxy xanthone |
| CN105837549A (en) * | 2016-04-18 | 2016-08-10 | 哈尔滨工业大学（威海） | Synthetic method of marine terpenoid natural product namely ent-chromazonarol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107266410A (en) * | 2017-07-29 | 2017-10-20 | 哈尔滨工业大学（威海） | A kind of 8 epi puupehedione synthetic method |
| CN107266410B (en) * | 2017-07-29 | 2020-01-03 | 威海创惠环保科技有限公司 | Synthesis method of 8-epi-puupehedione |
| CN109096114A (en) * | 2018-10-09 | 2018-12-28 | 哈尔滨工业大学（威海） | A kind of synthetic method of marine natural products smenodiol |
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