CN110218136A - Alkene and the coupling of one step of aldehyde efficiently synthesize E- allyl alcohol compound - Google Patents
Alkene and the coupling of one step of aldehyde efficiently synthesize E- allyl alcohol compound Download PDFInfo
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- CN110218136A CN110218136A CN201810173226.XA CN201810173226A CN110218136A CN 110218136 A CN110218136 A CN 110218136A CN 201810173226 A CN201810173226 A CN 201810173226A CN 110218136 A CN110218136 A CN 110218136A
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- boric acid
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- XXROGKLTLUQVRX-UHFFFAOYSA-N hydroxymethylethylene Natural products OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 3
- 150000001336 alkenes Chemical class 0.000 title claims description 4
- 230000008878 coupling Effects 0.000 title claims description 3
- 238000010168 coupling process Methods 0.000 title claims description 3
- 238000005859 coupling reaction Methods 0.000 title claims description 3
- 238000000034 method Methods 0.000 claims abstract description 19
- -1 aryl olefins Chemical class 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000002994 raw material Substances 0.000 claims description 26
- 235000019441 ethanol Nutrition 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 239000003863 metallic catalyst Substances 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 claims description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims 1
- HCIMXTXCDVBLOA-UHFFFAOYSA-N [4-(trifluoromethyl)phenoxy]boronic acid Chemical compound OB(O)OC1=CC=C(C(F)(F)F)C=C1 HCIMXTXCDVBLOA-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 22
- 230000015572 biosynthetic process Effects 0.000 abstract description 21
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- IBLNKMRFIPWSOY-FNORWQNLSA-N stiripentol Chemical compound CC(C)(C)C(O)\C=C\C1=CC=C2OCOC2=C1 IBLNKMRFIPWSOY-FNORWQNLSA-N 0.000 abstract description 3
- 229960001897 stiripentol Drugs 0.000 abstract description 3
- RIYVUZHFPDAAIC-UHFFFAOYSA-N Epidarlinine Natural products CN1CCCC1CC(O)C=Cc2ccccc2 RIYVUZHFPDAAIC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007868 Raney catalyst Substances 0.000 abstract description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000564 Raney nickel Inorganic materials 0.000 abstract description 2
- 125000003342 alkenyl group Chemical group 0.000 abstract description 2
- 229930014626 natural product Natural products 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007848 Bronsted acid Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 84
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 60
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 229910001873 dinitrogen Inorganic materials 0.000 description 20
- 239000003480 eluent Substances 0.000 description 20
- 238000001914 filtration Methods 0.000 description 20
- 239000003208 petroleum Substances 0.000 description 20
- 238000010898 silica gel chromatography Methods 0.000 description 20
- 239000007788 liquid Substances 0.000 description 15
- 239000012230 colorless oil Substances 0.000 description 10
- 150000001299 aldehydes Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 3
- SSLOCCVNUSYUIX-MDZDMXLPSA-N (e)-4,4-dimethyl-1-phenylpent-1-en-3-ol Chemical compound CC(C)(C)C(O)\C=C\C1=CC=CC=C1 SSLOCCVNUSYUIX-MDZDMXLPSA-N 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- ZPMKOKOZPFNDLZ-ACCUITESSA-N (E)-1,5-diphenylpent-1-en-3-ol Chemical compound C=1C=CC=CC=1/C=C/C(O)CCC1=CC=CC=C1 ZPMKOKOZPFNDLZ-ACCUITESSA-N 0.000 description 1
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 1
- ORACYDGVNJGDMI-VAWYXSNFSA-N (e)-1,3-diphenylprop-2-en-1-ol Chemical compound C=1C=CC=CC=1C(O)\C=C\C1=CC=CC=C1 ORACYDGVNJGDMI-VAWYXSNFSA-N 0.000 description 1
- BGPRHVUJVMHXCT-VAWYXSNFSA-N (e)-1-cyclohexyl-3-phenylprop-2-en-1-ol Chemical compound C1CCCCC1C(O)\C=C\C1=CC=CC=C1 BGPRHVUJVMHXCT-VAWYXSNFSA-N 0.000 description 1
- MPQYLVUGJQUTPM-CMDGGOBGSA-N (e)-1-phenylpent-1-en-3-ol Chemical compound CCC(O)\C=C\C1=CC=CC=C1 MPQYLVUGJQUTPM-CMDGGOBGSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 238000006405 Nozaki-Hiyama-Kishi reaction Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000003447 ipsilateral effect Effects 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006578 reductive coupling reaction Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- IPSRAFUHLHIWAR-UHFFFAOYSA-N zinc;ethane Chemical compound [Zn+2].[CH2-]C.[CH2-]C IPSRAFUHLHIWAR-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
- C07D317/20—Free hydroxyl or mercaptan
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
- C07D317/54—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of aryl olefins and simple aldehyde compound under cheap metal Raney nickel and bronsted acid co-catalysis, and the method for efficiently preparing allyl alcohol compound belongs to applied technical field.One of the main points that the present invention solves the problems, such as are to provide a kind of simple and practical method, can be from the allyl alcohol compound such as natural products (darlinine) and drug (stiripentol) of cheap aryl olefin and simple not activated aldehydes reagent synthesis high added value；The two of main points are to provide a kind of simple and fast method, can be to avoid the use of excessive alkenyl metal reagent.
Description
Technical field
The present invention relates to one kind from simple olefins and aldehyde, prepares the synthetic method of E- allyl alcohol compound, belongs to
Methodological study and applied technical field.
Background technique
Allyl alcohol compound is a kind of important intermediate in organic synthesis.Allyl alcohol structure is also widely present in simultaneously
In natural products and drug molecule, therefore the synthetic method that exploitation is simple and efficient has very high application value.In general, allyl alcohol
It can be synthesized by following two method:
A) carbonyls such as alkenyl metal reagent and aldehyde ketone progress addition obtains.(Shinokibo, H.；Oshima,
K.Eur.J.Org.Chem.2004,2081.) this method requirement stringent anhydrous and oxygen-free of reaction condition, alkylmetal reagent needs pre-
It first prepares, and alkylmetal reagent activity is high, excessive metal waste is generated in reaction process, Atom economy is lower and pollutes
Environment.
B) alkynes and aldehyde ketone carbonyls synthesize to obtain under metal catalytic by the method for transfer hydrogenation.(Ngai,
M.-Y.；Barchuk, A.；Krische, M.J.J.Am.Chem.Soc.2007,129,280；Huddleston, R.R.；Jang,
H.-Y.；Krische, M.J.J.Am.Chem.Soc.2003,125,11488) this method, alkynes cost of material is expensive, and reacts
Process generally requires noble metal catalyst, such as rhodium, iridium, ruthenium.It needs that excessive reducing agent is added in reaction process, improves anti-
The cost answered.
a)Direct addition of alkenylmetals to aldehyde
M=Mg (Grignard reagent), Li, Zn, (from alkenylhalide)；
M=Cr (Nozaki-Hiyama-Kishi reaction), (from alkenylhalide)；
M=B, Al, Zr, (from alkyne)；
B) Reductive coupling of alkyne with aldehyde (Montgomery, Jamison,
Krische et al.)
T.M.=Rh, Ir, Ni ... Reductant=Et3B, Et2Zn, H2, H donor ...
In conclusion existing synthetic method is not only although allyl alcohol is a kind of important organic reaction intermediate
It is required that operation is stringent, and complex steps, production cost is higher, and certain pollution can be generated to environment, so that scale metaplasia
Production faces many problems.
Summary of the invention
One of the objects of the present invention is to provide a kind of simple and practical methods, can try from cheap aldehyde and aryl olefin
Agent reaction preparation E- allyl alcohol compound；The second purpose is to provide a kind of simple and fast method, efficiently synthesizes natural production
Object (darlinine) and drug (stiripentol) etc..
1. a kind of method for efficiently preparing E- allyl alcohol by one-step method, it is characterised in that the specific steps of this method are as follows:
Raw material 1 and 2, Phosphine ligands, aryl boric acid, metallic catalyst and solvent are sequentially added in reaction flask, in nitrogen
In atmosphere, is stirred 16 hours under assigned temperature, be cooled to room temperature, solvent is removed under reduced pressure, column chromatography for separation obtains target product.
2 it is involved in the present invention to metallic catalyst be Ni (cod)2, the dosage of catalyst is generally 5-20mol%.
3 Phosphine ligands involved in the present invention arrived, can be tri-cyclopentylphosphine, tricyclohexyl phosphine, dosage is generally 15-
40mol%.
4 solvent for use of the present invention are alcohols solvents, can be methanol, ethyl alcohol, isopropanol, and dosage is for every mM of original
The corresponding use scope of material 2 is 5mL to 10mL.
5 it is involved in the present invention to reaction temperature can be carried out under the arbitrary temp in 25 DEG C to 75 DEG C.
R in 6 the raw materials used in the present invention 11Can for aryl, etc., R2It can be the substituent groups such as hydrogen, alkyl, aryl, heteroaryl
Group, but it is not limited to these groups.
The invention has the advantages that
1. various reagents used in the present invention can business gained, raw material sources are extensive, cheap, and various reagents room temperature
It can be stabilized under normal pressure, operation processing is convenient, without specially treated.
2, the present invention has carried out the experiment of gram quantity grade, reacts and is suitble to mass production.
3. operation of the present invention is easy, target product is can be obtained in single step reaction, avoids sky involved by previous methods
The hazardous agents such as gas and the extremely sensitive alkylmetal reagent of water, post-processing also have no special requirements, greatly reduce synthesis such
The production cost of compound.
4. used in the present invention is cheap Raney nickel, while keeping good catalytic effect, reducing cost, reach
It to simplified technique, reduces cost, facilitate postprocessing working procedures, the recycling of solvent is convenient, and reducing environmental pollution etc. requires.
Specific implementation method
Following implementation example will better illustrate the present invention, but need to will be it is emphasised that the present invention is by no means limited to these
Implement content represented by example.Following examples show not ipsilaterals of the invention.Given data include concrete operations and
Reaction condition and product.Product purity is identified by nuclear-magnetism.
Embodiment 1:(E) -1,5-diphenylpent-1-en-3-ol synthesis
It is sequentially added in reaction flask raw material 1a (104mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 16 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/5), obtains 98mg colorless oil
Shape liquid, yield 82%.1H NMR (400MHz, CDCl3) δ 7.41-7.15 (m, 10H), 6.57 (d, J=16.0Hz, 1H),
6.24 (dd, J=16.0,6.8Hz, 1H), 4.31-4.27 (m, 1H), 2.83-2.68 (m, 2H), 2.04-1.86 (m, 2H),
1.77 (br s, 1H)13C NMR (100MHz, CDCl3) δ 141.8,136.6,132.2,130.6,128.6,128.4,128.4,
127.7,126.4,125.8,72.3,38.7,31.7.
Embodiment 2:(E) -1-Phenylpent-1-en-3-ol synthesis
It is sequentially added in reaction flask raw material 1a (104mg, 1.0mmol), 2b (24mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 16 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/5), obtains 60mg colorless oil
Shape liquid, yield 74%.1H NMR (400MHz, CDCl3) δ 7.42-7.36 (m, 2H), 7.35-7.29 (m, 2H), 7.27-7.21
(m, 1H), 6.58 (d, J=16.0Hz, 1H), 6.22 (dd, J=16.0,6.8Hz, 1H), 4.24-4.19 (m, 1H), 1.76-
1.59 (m, 2H), 0.97 (t, J=7.2Hz, 2H)13C NMR (100MHz, CDCl3) δ 136.7,132.2,130.4,128.5,
127.6,126.4,74.4,30.3,9.7.
Embodiment 3:(E)-Isosorbide-5-Nitrae-Diphenylbut-3-en-2-ol synthesis
It is sequentially added in reaction flask raw material 1a (104mg, 1.0mmol), 2c (67mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 16 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/5), obtains 52mg colorless oil
Shape liquid, yield 46%.1H NMR (400MHz, CDCl3) δ 7.39-7.35 (m, 2H), 7.35-7.29 (m, 4H), 7.28-7.21
(m, 4H), 6.59 (d, J=16.0Hz, 1H), 6.28 (dd, J=16.0,6.0Hz, 1H), 4.60-4.47 (m, 1H), 2.97 (m,
2H), 1.76 (d, J=3.6Hz, 1H)13C NMR (100MHz, CDCl3) δ 137.6,136.7,131.4,130.4,129.6,
128.6,127.7,126.6,126.5,73.5,44.2.
Embodiment 4:(E) -1- (Benzyloxy) -4-phenylbut-3-en-2-ol synthesis
It is sequentially added in reaction flask raw material 1a (104mg, 1.0mmol), 2d (75mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 16 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/5), obtains 80mg colorless oil
Shape liquid, yield 63%.1H NMR (400MHz, CDCl3) δ 7.40-7.33 (m, 6H), 7.31 (t, J=7.6Hz, 3H), 7.26-
7.21 (m, 1H), 6.69 (d, J=16.0Hz, 1H), 6.18 (dd, J=16.0,6.0Hz, 1H), 4.60 (s, 2H), 4.52 (d, J
=6.4Hz, 1H), 3.62 (dd, J=9.6,3.2Hz, 1H), 3.51-3.40 (m, 1H), 2.58 (d, J=3.2Hz, 1H)13C
NMR (100MHz, CDCl3) δ 137.8,136.6,131.7,128.54,128.50,127.9,127.8,127.7,127.6,
126.5,74.1,73.4,71.4.
Embodiment 5:(E) -5- (4-Isopropylphenyl) -4-methyl-1-phenylpent-1-en-3-ol conjunction
At
It is sequentially added in reaction flask raw material 1a (104mg, 1.0mmol), 2e (95mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 16 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/5), and it is colourless to obtain 100mg
Oily liquids, yield 63%.1H NMR (400MHz, CDCl3) 1: 1 mixture of diastereomers: δ of for the
7.39-7.35 (m, 2H), 7.33-7.27 (m, 2H), 7.26-7.20 (m, 1H), 7.15-7.10 (m, 4H), 6.57 (d, J=
16.0Hz, 1H), 6.18 (dd, J=15.6,2.8Hz, 0.56H), 6.16 (dd, J=15.6,2.0Hz, 0.44H), 4.17-
4.10 (m, 0.48H), 4.10-4.00 (m, 0.52H), 2.91-2.83 (m, 2H), 2.43-2.36 (m, 1H), 2.08-1.93 (m,
1H), (dd, J=12.6,6.8Hz, 3H) of 1.81 (br s, 1H), 1.24 (d, J=6.8Hz, 6H), 0.9013C NMR
(100MHz, CDCl3) δ 146.3,146.3,138.1,137.9,136.8,136.7,131.6,131.1,130.7,130.2,
129.1,129.0,128.6,128.5,127.62,127.5,126.4,126.4,126.3,126.2,76.5,75.5,41.1,
38.8,38.5,33.6,24.0,15.1,14.2.
Embodiment 6:(E) -1-Cyclohexyl-3-phenylprop-2-en-1-ol synthesis
It is sequentially added in reaction flask raw material 1a (104mg, 1.0mmol), 2f (56mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 16 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, diatomite filtering, silica gel column chromatography, and eluent is (ethyl acetate/petroleum ether=1/5), and it is solid to obtain 60mg white
Body, yield 56%.1H NMR (400MHz, CDCl3): δ 7.38 (d, J=8.0Hz, 2H), 7.31 (t, J=7.4Hz, 2H),
7.26-7.20 (m, 1H), 6.54 (d, J=16.0Hz, 1H), 6.23 (dd, J=15.8,7.2Hz, 1H), 4.01 (t, J=
6.6Hz, 1H), 1.91 (d, J=12.4Hz, 1H), 1.79-1.66 (m, 5H), 1.54-1.46 (m, 1H), 1.34-0.97 (m,
5H).13C NMR (100MHz, CDCl3) δ 136.8,131.2,131.0,128.5,127.5,126.4,77.6,43.9,28.9,
28.6,26.5,26.1,26.0.
Embodiment 7:(E) -1- ((R) -2,2-Dimethyl-1,3-dioxolan-4-yl) -3-phenylprop-2-en-
The synthesis of 1-ol (3m)
It is sequentially added in reaction flask raw material 1a (104mg, 1.0mmol), 2g (65mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 20 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, diatomite filtering, silica gel column chromatography, and eluent is (ethyl acetate/petroleum ether=1/5), obtains 101mg white
Solid, yield 86%.1H NMR (400MHz, CDCl3) 1.7: 1 mixture of diastereomers: δ of for the
7.40-7.35 (m, 2H), 7.33-7.30 (m, 2H), 7.28-7.22 (m, 1H), 6.71 (dd, J=15.8,1.0Hz, 0.6H),
6.70 (d, J=15.8Hz, 0.4H), 6.20-6.10 (m, 1H), 4.47 (s, 1H), 4.21 (m, 1H), 4.04-3.93 (m,
1.8H), 3.83 (m, 0.4H), 2.63 (m, 0.36H), 2.41 (d, J=2.6Hz, 0.62H), 1.47 (d, J=2.8Hz, 3H),
1.37 (s, 3H)13C NMR (100MHz, CDCl3) δ 136.3,136.2,133.1,132.0,128.5,128.0,127.8,
127.0,126.7,126.6,126.5,109.9,109.5,78.8,78.3,74.1,71.7,65.9,64.8,26.8,26.4,
25.3,25.1.HRMS (ESI) Calcd for [C14H17O2, (M+H)-H2O]+: 217.1223, Found:217.1219.
Embodiment 8:(E) -4,4-Dimethyl-1-phenylpent-1-en-3-ol (3o) synthesis
It is sequentially added in reaction flask raw material 1a (104mg, 1.0mmol), 2h (43mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 20 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, diatomite filtering, silica gel column chromatography, and eluent is (ethyl acetate/petroleum ether=1/5), and it is solid to obtain 48mg white
Body, yield 50%.1H NMR (400MHz, CDCl3) δ 7.42-7.36 (m, 2H), 7.32 (m, 2H), 7.24 (m, 1H), 6.58 (d,
J=16.0Hz, 1H), 6.29 (dd, J=16.0,7.2Hz, 1H), 3.93 (dd, J=7.2,2.8Hz, 1H), 1.57 (s, 1H),
0.97 (s, 9H)13C NMR (100MHz, CDCl3) δ 136.8,131.8,129.5,128.6,127.6,126.4,81.0,
35.3 25.8.
Embodiment 9:(E) -3-Phenylprop-2-en-1-ol synthesis
It is sequentially added in reaction flask raw material 1a (208mg, 2.0mmol), 2i (15mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 24 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, diatomite filtering, silica gel column chromatography, and eluent is (ethyl acetate/petroleum ether=1/5), and it is solid to obtain 31mg white
Body, yield 45%.1H NMR (400MHz, CDCl3) δ 7.25 (d, J=7.6Hz, 2H), 7.18 (t, J=7.4Hz, 2H), 7.11
(d, J=7.2Hz, 1H), 6.48 (d, J=15.8Hz, 1H), 6.23 (dt, J=15.8,5.6Hz, 1H), 4.18 (d, J=
5.4Hz, 2H), 1.47 (s, 1H)13C NMR (100MHz, CDCl3) δ 136.7,131.1,128.6,128.5,127.7,
126.4,63.7.
Embodiment 10:(E) -1,3-Diphenylprop-2-en-1-ol synthesis
It is sequentially added in reaction flask raw material 1a (104mg, 1.0mmol), 2j (53mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 24 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/5), obtains 25mg colorless oil
Shape liquid, yield 24%.1H NMR (400MHz, CDCl3) δ 7.46-7.21 (m, 10H), 6.69 (d, J=15.6Hz, 1H),
6.39 (dd, J=15.6,6.4Hz, 1H), 5.39 (dd, J=6.2,3.6Hz, 1H), 2.04 (d, J=3.6Hz, 1H)13C NMR
(100MHz, CDCl3) δ 142.7,136.5,131.5,130.6,128.6,128.6,127.8,127.8,126.6,126.3,
75.1.7 126.4,63.7.
Embodiment 11:(E) -1- (4-Methoxyphenyl) -5-phenylpent-1-en-3-ol synthesis
It is sequentially added in reaction flask raw material 1b (134mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 24 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/5), and it is colourless to obtain 106mg
Oily liquids, yield 79%.1H NMR (400MHz, CDCl3) δ 7.41-7.27 (m, 5H), 7.25-7.18 (m, 3H), 6.87 (d,
J=8.4Hz, 2H), 6.53 (d, J=16.0Hz, 1H), 6.12 (dd, J=16.0,7.2Hz, 1H), 4.29-4.24 (m, 1H),
3.80 (s, 3H), 2.81-2.69 (m, 2H), 2.04-1.88 (m, 2H), 1.77 (s, 1H)13C NMR (100MHz, CDCl3)δ
159.3,141.8,130.2,129.9,129.3,128.4,128.4,127.6,125.8,114.0,72.5,55.3,38.8,
31.7.HRMS(ESI)Calcd for[C18H19O, (M+H)-H2O]+: 251.1430, Found:251.1436.
Embodiment 12:(E) -1- (3-Methoxyphenyl) -5-phenylpent-1-en-3-ol synthesis
It is sequentially added in reaction flask raw material 1c (134mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 24 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/5), obtains 54mg colorless oil
Shape liquid, yield 40%.1H NMR (400MHz, CDCl3) δ 7.37-7.27 (m, 2H), 7.25-7.16 (m, 4H), 6.99 (d, J
=7.6Hz, 1H), 6.91 (s, 1H), 6.82 (dd, J=8.0,2.4Hz, 1H), 6.56 (d, J=16.0Hz, 1H), 6.25 (dd,
J=16.0,6.8Hz, 1H), 4.37-4.25 (m, 1H), 3.83 (s, 3H), 2.84-2.71 (m, 2H), 2.05-1.89 (m, 2H),
1.74 (br s, 1H)13C NMR (100MHz, CDCl3) δ 159.8,141.7,138.1,132.5,130.4,129.6,128.4,
128.4,125.9,119.1,113.3,111.7,72.2,55.2,38.7,31.7.
Embodiment 13:(E) -1- (2-Methoxyphenyl) -5-phenylpent-1-en-3-ol synthesis
It is sequentially added in reaction flask raw material 1d (134mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 24 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/5), obtains 94mg colorless oil
Shape liquid, yield 70%.1H NMR (400MHz, CDCl3) δ 7.42 (d, J=7.6Hz, 1H), 7.30-7.16 (m, 6H), 6.93-
6.85 (m, 3H), 6.24 (dd, J=16.0,7.2Hz, 1H), 4.32-4.27 (m, 1H), 3.83 (s, 3H), 2.84-2.66 (m,
2H), 2.04-1.86 (m, 2H), 1.80 (br s, 1H)13C NMR (100MHz, CDCl3) δ 156.7,141.9,132.8,
128.7,128.5,128.3,126.9,125.8,125.6,125.5,120.6,110.8,72.8,55.4,38.7,31.7
Embodiment 14:(E) -1- (4- (Benzyloxy) phenyl) -5-phenylpent-1-en-3-ol synthesis
It is sequentially added in reaction flask raw material 1e (210mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 24 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/5), and it is colourless to obtain 132mg
Oily liquids, yield 77%.1H NMR (400MHz, CDCl3) δ 7.46-7.36 (m, 4H), 7.36-7.27 (m, 5H), 7.25-
7.17 (m, 3H), 6.96-6.91 (m, 2H), 6.52 (d, J=16.0Hz, 1H), 6.12 (dd, J=16.0,7.2Hz, 1H),
5.08 (s, 2H), 4.34-4.23 (m, 1H), 2.89-2.64 (m, 2H), 2.08-1.85 (m, 2H), 1.61 (d, J=3.2Hz,
1H).13C NMR (100MHz, CDCl3) δ 158.4,141.8,136.8,130.1,130.1,129.6,128.5,128.42,
128.35,128.0,127.6,127.4,125.8,114.9,72.4,70.0,38.7,31.7.HRMS (ESI) Calcd for
[C24H23, (M+H)-H2O]+: 311.1743, Found:327.1744.
Embodiment 15:(E) -1- (4- (Dimethylamino) phenyl) -5-phenylpent-1-en-3-ol synthesis
It is sequentially added in reaction flask raw material 1f (147mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 24 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/5), and it is faint yellow to obtain 67mg
Oily liquids, yield 50%.1H NMR (400MHz, CDCl3) δ 7.32-7.26 (m, 4H), 7.25-7.16 (m, 3H), 6.69 (d,
J=8.0Hz, 2H), 6.49 (d, J=16.0Hz, 1H), 6.05 (dd, J=15.2,6.4Hz, 1H), 4.30-4.23 (m, 1H),
2.97 (s, 6H), 2.80-2.68 (m, 2H), 2.04-1.85 (m, 2H), 1.56 (s, 1H)13C NMR (100MHz, CDCl3)δ
150.1,142.0,130.9,128.4,128.3,127.8,127.4,125.7,125.0,112.4,72.7,40.4,38.8,
31.8.HRMS(ESI)Calcd for[C19H24NO, M+H]+: 282.1852, Found:282.1853.
Embodiment 16:(E) -5-Phenyl-1- (p-tolyl) pent-1-en-3-ol synthesis
It is sequentially added in reaction flask raw material 1g (118mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 24 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/5), obtains 93mg colorless oil
Shape liquid, yield 74%.1H NMR (400MHz, CDCl3) δ 7.32-7.28 (m, 4H), 7.25-7.17 (m, 3H), 7.15-7.09
(m, 2H), 6.55 (d, J=15.6Hz, 1H), 6.20 (dd, J=16.0,6.8Hz, 1H), 4.35-4.23 (m, 1H), 2.86-
2.67 (m, 2H), 2.35 (s, 3H), 2.06-1.85 (m, 2H), 1.65 (br s, 1H)13C NMR (100MHz, CDCl3)δ
141.8,137.6,133.8,131.1,130.5,129.3,128.4,128.4,126.4,125.8,72.4,38.7,31.7,
21.2.
Embodiment 17:(E) -1- (2,5-Dimethylphenyl) -5-phenylpent-1-en-3-ol synthesis
It is sequentially added in reaction flask raw material 1h (132mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 24 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/5), obtains 80mg colorless oil
Shape liquid, yield 60%.1H NMR (400MHz, CDCl3) δ 7.31-7.25 (m, 2H), 7.24-7.17 (m, 4H), 7.02-6.95
(m, 2H), 6.75 (d, J=15.6Hz, 1H), 6.10 (dd, J=16.0,6.8Hz, 1H), 4.34-4.24 (m, 1H), 2.75-
2.69 (m, 2H), 2.31 (s, 3H), 2.30 (s, 3H), 2.07-1.86 (m, 2H), 1.71 (br s, 1H)13C NMR (100MHz,
CDCl3) δ 141.8,135.5,135.4,133.3,132.4,130.2,128.6,128.5,128.4,126.3,125.9,
72.57,38.77,31.7,21.0,19.3.HRMS (ESI) Calcd for [C19H21, (M+H)-H2O]+: 249.1638,
Found:249.1629.
Embodiment 18:(E) -1- (4-Fluorophenyl) -5-phenylpent-1-en-3-ol synthesis
It is sequentially added in reaction flask raw material 1i (122mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 24 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/10), and it is colourless to obtain 101mg
Oily liquids, yield 79%.1H NMR (400MHz, CDCl3) δ 7.31-7.27 (m, 2H), 7.25-7.19 (m, 2H), 7.18-
7.11 (m, 3H), 6.98-6.90 (m, 2H), 6.48 (d, J=15.6Hz, 1H), 6.10 (dd, J=15.6,6.8Hz, 1H),
4.24-4.19 (m, 1H), 2.80-2.60 (m, 2H), 1.98-1.81 (m, 2H), 1.62 (br s, 1H)13C NMR (100MHz,
CDCl3) δ 161.3 (d, J=246.7Hz), 140.7,131.7 (d, J=3.2Hz), 130.9 (d, J=1.8Hz), 128.4,
127.43,127.41,126.9 (d, J=8.1Hz), 124.9,114.5 (d, J=21.6Hz), 71.2,37.7,30.7.19F
NMR (376MHz, CDCl3)δF- 114.0 (s, ArF) .HRMS (ESI) Calcd for [C17H16F, (M+H)-H2O]+:
239.1231, Found:239.1223.
Embodiment 19:(E) -1- (2-Fluorophenyl) -5-phenylpent-1-en-3-ol synthesis
It is sequentially added in reaction flask raw material 1j (122mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 24 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, and diatomite filtering, silica gel column chromatography, eluent is (ethyl acetate/petroleum ether=1/5), obtains 91mg colorless oil
Shape liquid, yield 71%.1H NMR (400MHz, CDCl3) δ 7.45 (t, J=7.6Hz, 1H), 7.31-7.20 (m, 6H), 7.11-
7.01 (m, 2H), 6.75 (d, J=16.4Hz, 1H), 6.34 (dd, J=16.0,6.4Hz, 1H), 4.36-4.27 (m, 1H),
2.90-2.65 (m, 2H), 2.08-1.87 (m, 2H), 1.73 (br s, 1H)13C NMR (100MHz, CDCl3) δ 160.3 (d, J
=249.3Hz), 141.7,134.8 (d, J=4.7Hz), 128.9 (d, J=8.4Hz), 128.4 (d, J=4.8Hz), 127.5
(d, J=3.7Hz), 125.9,124.4,124.3,124.1 (d, J=3.6Hz), 122.9 (d, J=3.6Hz), 115.7 (d, J
=22.1Hz), 72.4,38.6,31.7.19F NMR (376MHz, CDCl3)δF- 117.7 (s, ArF) .HRMS (ESI) Calcd
for[C17H16F, (M+H)-H2O]+: 239.1231, Found:239.1236
The synthesis of embodiment 20:Stiripentol
It is sequentially added in reaction flask raw material 5 (148mg, 1.0mmol), 6 (43mg, 0.5mmol), Ni (cod)2
(13.8mg, 0.05mmol), PhB (OH)275 DEG C, it is small to react 24 for (12.2mg, 0.1mmol), ethyl alcohol (2mL) under condition of nitrogen gas
When.Reaction terminates, diatomite filtering, silica gel column chromatography, and eluent is (ethyl acetate/petroleum ether=1/5), and it is solid to obtain 59mg white
Body, yield 50%.1H NMR (400MHz, CDCl3) δ 6.94 (s, 1H), 6.82 (d, J=8.0Hz, 1H), 6.76 (d, J=
8.0.Hz, 1H), 6.48 (d, J=15.6Hz, 1H), 6.11 (dd, J=15.6,7.2Hz, 1H), 5.95 (s, 2H), 3.89 (d, J
=6.8Hz, 1H), 0.96 (s, 9H)13C NMR (100MHz, CDCl3) δ 148.0,147.2,131.5,131.3,127.7,
121.1,108.3,105.7,101.1,81.0,35.3,25.8.
Claims (7)
1. alkene and the coupling of one step of aldehyde efficiently synthesize E- allyl alcohol compound, it is characterised in that the specific steps of this method are as follows:
Raw material 1 and 2, Phosphine ligands, aryl boric acid, metallic catalyst and solvent are sequentially added in reaction flask, in nitrogen atmosphere
In, it is stirred 16 hours under assigned temperature, is cooled to room temperature, solvent is removed under reduced pressure, column chromatography for separation obtains target product.
2. it is involved in the present invention to metallic catalyst be Ni (cod)2, the dosage of catalyst is generally 5-20mol%.
3. the Phosphine ligands involved in the present invention arrived, can be tri-cyclopentylphosphine, tricyclohexyl phosphine, dosage is generally 15-
40mol%.
4. it is involved in the present invention to additive be it is related to aryl boric acid, can be with phenyl boric acid, pentafluorophenyl boric acid, 4- trifluoromethyl
Phenyl boric acid.
5. solvent for use of the present invention is alcohols solvent, methanol, ethyl alcohol, isopropanol can be, dosage is for every mM of raw material 2
Corresponding use scope is 5mL to 10mL.
6. it is involved in the present invention to reaction temperature can be carried out under the arbitrary temp in 25 DEG C to 75 DEG C.
7. R in the raw materials used in the present invention 11Can for aryl, etc., R2It can be the substituent groups such as hydrogen, alkyl, aryl, heteroaryl,
But it is not limited to these groups.
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| 郑彦龙等: "铁催化的区域选择性的非活化烯烃和简单醛类的转移氢化偶联", 《中国化学会第30届学术年会摘要集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591281A (en) * | 2022-03-21 | 2022-06-07 | 河南师范大学 | Preparation method of allyl alcohol compound |
| CN114591281B (en) * | 2022-03-21 | 2023-09-29 | 河南师范大学 | Preparation method of allyl alcohol compound |
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