CN110218136B - One-step coupling of olefin and aldehyde to efficiently synthesize E-allyl alcohol compound - Google Patents
One-step coupling of olefin and aldehyde to efficiently synthesize E-allyl alcohol compound Download PDFInfo
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- CN110218136B CN110218136B CN201810173226.XA CN201810173226A CN110218136B CN 110218136 B CN110218136 B CN 110218136B CN 201810173226 A CN201810173226 A CN 201810173226A CN 110218136 B CN110218136 B CN 110218136B
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- olefin
- allyl alcohol
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- aldehyde
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 7
- 150000001336 alkenes Chemical class 0.000 title claims description 8
- 230000008878 coupling Effects 0.000 title claims description 8
- 238000010168 coupling process Methods 0.000 title claims description 8
- 238000005859 coupling reaction Methods 0.000 title claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- -1 aryl olefin Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 24
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 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
- 239000004327 boric acid Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 3
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 claims description 3
- VASOMTXTRMYSKD-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boronic acid Chemical compound OB(O)C1=C(F)C(F)=C(F)C(F)=C1F VASOMTXTRMYSKD-UHFFFAOYSA-N 0.000 claims description 2
- HTFXWAOSQODIBI-UHFFFAOYSA-N 2-benzyl-1,3-dihydropyrrolo[3,4-c]pyridine Chemical compound C1C2=CC=NC=C2CN1CC1=CC=CC=C1 HTFXWAOSQODIBI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001543 aryl boronic acids Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 238000001816 cooling 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 class [H]* 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 150000004808 allyl alcohols Chemical class 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 229930014626 natural product Natural products 0.000 abstract description 3
- RIYVUZHFPDAAIC-UHFFFAOYSA-N Epidarlinine Natural products CN1CCCC1CC(O)C=Cc2ccccc2 RIYVUZHFPDAAIC-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003342 alkenyl group Chemical group 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000007848 Bronsted acid Substances 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 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- 239000000203 mixture Substances 0.000 description 21
- 239000007858 starting material Substances 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 20
- 239000003480 eluent Substances 0.000 description 20
- 239000003208 petroleum Substances 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 15
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 10
- 238000010898 silica gel chromatography Methods 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical group OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 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
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- XYWDLGMMAUGKPJ-VAWYXSNFSA-N (E)-4-phenyl-1-phenylmethoxybut-3-en-2-ol Chemical compound OC(COCc1ccccc1)\C=C\c1ccccc1 XYWDLGMMAUGKPJ-VAWYXSNFSA-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
- RFSWZRZQZYKWQT-VAWYXSNFSA-N (e)-1,4-diphenylbut-3-en-2-ol Chemical compound C=1C=CC=CC=1/C=C/C(O)CC1=CC=CC=C1 RFSWZRZQZYKWQT-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
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- 239000007818 Grignard reagent Substances 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
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 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
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006578 reductive coupling reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 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
- IBLNKMRFIPWSOY-FNORWQNLSA-N stiripentol Chemical compound CC(C)(C)C(O)\C=C\C1=CC=C2OCOC2=C1 IBLNKMRFIPWSOY-FNORWQNLSA-N 0.000 description 1
- 229960001897 stiripentol Drugs 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
- 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 invention provides a method for efficiently preparing allyl alcohol compounds by aryl olefin and simple aldehyde compounds under the co-catalysis of a cheap metal nickel catalyst and Bronsted acid, belonging to the technical field of application. One of the points of solving the problems of the present invention is to provide a simple and practical method which can synthesize high value-added allyl alcohols such as natural products (darlinine) and drugs (stiipentol) from inexpensive aryl olefins and simple, unactivated aldehyde reagents; the second point is to provide a simple and fast method, which can avoid the use of excessive alkenyl metal reagent.
Description
Technical Field
The invention relates to a synthetic method for preparing an E-allyl alcohol compound from simple monoolefin and aldehyde, belonging to the technical field of methodology research and application.
Background
Allyl alcohol compounds are an important class of intermediates in organic synthesis. Meanwhile, the allyl alcohol structure also widely exists in natural products and drug molecules, so that the development of a simple and efficient synthetic method has high application value. In general, allyl alcohol can be synthesized by the following two methods:
a) an alkenyl metal reagent and a carbonyl compound such as an aldehyde ketone. (Shinokibo, H.; Oshima, K.Eur.J.org.chem.2004, 2081.) the process requires strict anhydrous and oxygen-free reaction conditions, the alkyl metal reagent needs to be prepared in advance, and the alkyl metal reagent has high activity, generates excessive metal waste during the reaction, has low atom economy and pollutes the environment.
b) Alkyne and aldehyde ketone carbonyl compounds are synthesized by a transfer hydrogenation method under the catalysis of metal. (Ngai, M. -Y.; Barchuk, A.; Krische, M.J.J.Am.Chem.Soc.2007, 129, 280; Huddleston, R.R.; Jang, H. -Y.; Krische, M.J.Am.Chem.Soc.2003, 125, 11488) this process, alkyne starting materials are expensive, and the reaction process generally requires a noble metal catalyst such as rhodium, iridium, ruthenium, etc. Excessive reducing agent needs to be added in the reaction process, so that the reaction cost is increased.
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, although allyl alcohol is an important organic reaction intermediate, the existing synthetic method not only requires strict operation, but also has complex steps and higher production cost, and can cause certain pollution to the environment, so that the large-scale production faces a plurality of problems.
Disclosure of Invention
It is an object of the present invention to provide a simple and practical process for preparing an E-allylic alcohol compound from an inexpensive aldehyde and an aryl olefin reagent; the second purpose is to provide a simple and rapid method for efficiently synthesizing natural products (darlinine) and medicines (stiripentol).
The preparation method for synthesizing the E-allyl alcohol compound by one-step coupling of olefin and aldehyde comprises the following steps:
sequentially adding raw materials 1 and 2, a phosphine ligand, arylboronic acid, a nickel catalyst and a solvent into a reaction bottle, stirring for 16 hours at a specified temperature in a nitrogen atmosphere, cooling to room temperature, removing the solvent under reduced pressure, and performing column chromatography separation to obtain a target product 3; r in the raw material 1 and the product 31Is aryl; r in the raw material 2 and the product 32Is hydrogen, alkyl, aryl or heteroaryl.
Preferably, the nickel catalyst is Ni (cod)2The amount is generally 5 to 20 mol% of the raw material 2.
Preferably, the phosphine ligand is one or more of tricyclopentylphosphine and tricyclohexylphosphine, and the dosage of the phosphine ligand is 15-40 mol% of the raw material 2.
Preferably, the solvent is an alcoholic solvent, which may be methanol, ethanol, isopropanol, in an amount corresponding to a use range of 5mL to 10mL per millimole of starting material 2.
Preferably, the specified temperature is any of 25 ℃ to 75 ℃.
Preferably, the aryl boric acid is one or more of phenylboronic acid, pentafluorophenylboronic acid or 4-trifluoromethylphenylboronic acid, and the amount of the aryl boric acid is generally 5 to 50 mol% of the raw material 2.
The invention has the advantages that:
1. the invention has the advantages of commercial availability of various reagents, wide raw material source, low price, stable existence of various reagents at normal temperature and normal pressure, convenient operation and treatment and no need of special treatment.
2. The invention carries out gram-magnitude experiments, and the reaction is suitable for mass production.
3. The method is simple and convenient to operate, the target product can be obtained through one-step reaction, dangerous reagents such as air and extremely sensitive alkyl metal reagents and the like related to the conventional method are avoided, no special requirement is required for post-treatment, and the production cost for synthesizing the compounds is greatly reduced.
4. The invention uses cheap nickel catalyst, which can simplify the process, reduce the cost, facilitate the post-treatment process, recycle the solvent and reduce the environmental pollution while maintaining the good catalytic effect and reducing the cost.
Detailed description of the invention
The following examples will better illustrate the invention, but it should be emphasized that the invention is in no way limited to what is shown in these examples. The following examples show different aspects of the invention. The data presented include specific operating and reaction conditions and products. The purity of the product was identified by nuclear magnetism.
Example 1: (E) synthesis of (E) -1, 5-diphenylpen-1-en-3-ol
The reaction flask was charged with the starting materials 1a (104mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 16 hours. After the reaction, the mixture was filtered through celite, and the resulting product was chromatographed on silica gel with eluent (ethyl acetate/petroleum ether: 1/5) to give 98mg of a colorless oily liquid in a yield of 82%.1H NMR(400MHz，CDCl3)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)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.
Example 2: (E) synthesis of (E) -1-Phenylpent-1-en-3-ol
The starting materials 1a (104mg, 1.0mmol), 2b (24mg, 0.5mmol), Ni (cod) were charged into a reaction flask in this order2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 16 hours. After the reaction, the mixture was filtered through celite, and the resulting product was chromatographed on silica gel with eluent (ethyl acetate/petroleum ether: 1/5) to give 60mg of colorless oily liquid with a yield of 74%.1H NMR(400MHz，CDCl3)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)136.7，132.2，130.4，128.5，127.6，126.4，74.4，30.3，9.7.
Example 3: (E) synthesis of (E) -1, 4-Diphenylbut-3-en-2-ol
The reaction flask was charged with the starting materials 1a (104mg, 1.0mmol), 2c (67mg, 0.5mmol), Ni (cod)2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 16 hours. After the reaction, the mixture was filtered through celite, and the resulting filtrate was purified by silica gel column chromatography with eluent (ethyl acetate/petroleum ether: 1/5) to give 52mg of a colorless oily liquid in a yield of 46%.1H NMR(400MHz，CDCl3)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)137.6，136.7，131.4，130.4，129.6，128.6，127.7，126.6，126.5，73.5，44.2.
Example 4: (E) synthesis of (E) -1- (Benzyloxy) -4-phenylbut-3-en-2-ol
The starting materials 1a (104mg, 1.0mmol), 2d (75mg, 0.5mmol), Ni (cod) were charged into a reaction flask in this order2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 16 hours. After the reaction, the mixture was filtered through celite, and the resulting product was chromatographed on silica gel with eluent (ethyl acetate/petroleum ether: 1/5) to give 80mg of a colorless oily liquid in a yield of 63%.1H NMR(400MHz，CDCl3)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).13CNMR(100MHz，CDCl3)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.
Example 5: (E) synthesis of (E) -5- (4-Isopropylphenyl) -4-methyl-1-phenylpent-1-en-3-ol
The starting materials 1a (104mg, 1.0mmol), 2e (95mg, 0.5mmol), Ni (cod) were charged in this order into a reaction flask2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 16 hours. After the reaction, the mixture was filtered through celite, and the resulting filtrate was purified by silica gel column chromatography with eluent (ethyl acetate/petroleum ether: 1/5) to give 100mg of colorless oily liquid in a yield of 63%.1H NMR(400MHz，CDCl3)for the 1∶1 mixture of diastereomers：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)，1.81(br s，1H)，1.24(d，J＝6.8Hz，6H)，0.90(dd，J＝12.6，6.8Hz，3H).13C NMR(100MHz，CDCl3)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.
Example 6: (E) synthesis of (E) -1-cyclohexenyl-3-phenylprop-2-en-1-ol
The starting materials 1a (104mg, 1.0mmol), 2f (56mg, 0.5mmol), Ni (cod) were charged into a reaction flask in this order2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 16 hours. After the reaction, the mixture was filtered through celite, and the resulting product was chromatographed on silica gel with eluent (ethyl acetate/petroleum ether: 1/5) to give 60mg of a white solid with a yield of 56%.1H NMR(400MHz，CDCl3)：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)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.
Example 7: (E) synthesis of (E) -1- ((R) -2, 2-Dimethyl-1, 3-dioxolan-4-yl) -3-phenylprop-2-en-1-ol (3m)
The starting materials 1a (104mg, 1.0mmol), 2g (65mg, 0.5mmol), Ni (cod) were charged in this order into a reaction flask2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 20 hours. After the reaction, the mixture was filtered through celite, and the resulting filtrate was purified by silica gel column chromatography with eluent (ethyl acetate/petroleum ether: 1/5) to obtain 101mg of a white solid with a yield of 86%.1H NMR(400MHz，CDCl3)for the 1.7∶1 mixture of diastereomers：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)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.
Example 8: (E) synthesis of (E) -4, 4-Dimethyl-1-phenylpent-1-en-3-ol (3o)
The starting materials 1a (104mg, 1.0mmol), 2h (43mg, 0.5mmol), Ni (cod) were charged into a reaction flask in this order2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 20 hours. After the reaction, the mixture was filtered through celite, and the resulting filtrate was chromatographed on silica gel with eluent (ethyl acetate/petroleum ether: 1/5) to give 48mg of a white solid with a yield of 50%.1H NMR(400MHz，CDCl3)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)136.8，131.8，129.5，128.6，127.6，126.4，81.0，35.3，25.8.
Example 9: (E) synthesis of (E) -3-Phenylprop-2-en-1-ol
The starting materials 1a (208mg, 2.0mmol), 2i (15mg, 0.5mmol), Ni (cod) were charged in this order in a reaction flask2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 24 hours. After the reaction, the mixture was filtered through celite, and the resulting product was chromatographed on silica gel with an eluent (ethyl acetate/petroleum ether: 1/5) to give 31mg of a white solid with a yield of 45%.1H NMR(400MHz，CDCl3)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)136.7，131.1，128.6，128.5，127.7，126.4，63.7.
Example 10: (E) synthesis of (E) -1, 3-Diphenylprop-2-en-1-ol
The starting materials 1a (104mg, 1.0mmol), 2j (53mg, 0.5mmol), Ni (cod) were charged in this order into a reaction flask2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 24 hours. After the reaction, the mixture was filtered through celite, and the resulting product was chromatographed on silica gel with eluent (ethyl acetate/petroleum ether: 1/5) to give 25mg of colorless oily liquid with a yield of 24%.1H NMR(400MHz，CDCl3)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)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.
Example 11: (E) synthesis of (E) -1- (4-Methoxyphenyl) -5-phenylpent-1-en-3-ol
The reaction flask was charged with the starting materials 1b (134mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, nitrogenAnd reacting for 24 hours under the condition. After the reaction, the mixture was filtered through celite, and the resulting filtrate was purified by silica gel column chromatography with eluent (ethyl acetate/petroleum ether: 1/5) to give 106mg of a colorless oily liquid in 79% yield.1H NMR(400MHz，CDCl3)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)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.
Example 12: (E) synthesis of (E) -1- (3-Methoxyphenyl) -5-phenylpent-1-en-3-ol
The reaction flask was charged with the starting materials 1c (134mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 24 hours. After the reaction, the mixture was filtered through celite, and the resulting filtrate was chromatographed on silica gel with an eluent (ethyl acetate/petroleum ether: 1/5) to give 54mg of a colorless oily liquid with a yield of 40%.1H NMR(400MHz，CDCl3)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)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.
Example 13: (E) synthesis of (E) -1- (2-Methoxyphenyl) -5-phenylpent-1-en-3-ol
The reaction flask was charged with the starting materials 1d (134mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 24 hours. After the reaction, the mixture was filtered through celite, and the resulting filtrate was purified by silica gel column chromatography with eluent (ethyl acetate/petroleum ether: 1/5) to obtain 94mg of a colorless oily liquid in a yield of 70%.1H NMR(400MHz，CDCl3)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)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
Example 14: (E) synthesis of (E) -1- (4- (Benzyloxy) phenyl) -5-phenylpent-1-en-3-ol
The starting materials 1e (210mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod) were charged in this order into a reaction flask2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 24 hours. After the reaction, the reaction mixture was filtered through celite, and the resulting filtrate was subjected to silica gel column chromatography with an eluent (ethyl acetate/petroleum ether: 1/5) to give 132mg of a colorless oily liquid in a yield of 77%.1H NMR(400MHz，CDCl3)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)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.
Example 15: (E) synthesis of (E) -1- (4- (dimethyllamino) phenyl) -5-phenylpent-1-en-3-ol
The reaction flask was charged with the starting materials 1f (147mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 24 hours. After the reaction, the mixture was filtered through celite, and the resulting product was chromatographed on silica gel with an eluent (ethyl acetate/petroleum ether: 1/5) to give 67mg of a pale yellow oily liquid in a yield of 50%.1H NMR(400MHz，CDCl3)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)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.
Example 16: (E) synthesis of (E) -5-Phenyl-1- (p-tolyl) pen-1-en-3-ol
The reaction flask was charged with 1g (118mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 24 hours. After the reaction, the mixture was filtered through celite, and the resulting product was chromatographed on silica gel with an eluent (ethyl acetate/petroleum ether: 1/5) to give 93mg of a colorless oily liquid with a yield of 74%.1H NMR(400MHz，CDCl3)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)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.
Example 17: (E) synthesis of (E) -1- (2, 5-Dimethylphenyl) -5-phenylpent-1-en-3-ol
The starting materials 1h (132mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod) were charged in this order to a reaction flask2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 24 hours. After the reaction, the mixture was filtered through celite, and the resulting product was chromatographed on silica gel with eluent (ethyl acetate/petroleum ether: 1/5) to give 80mg of colorless oily liquid with a yield of 60%.1H NMR(400MHz，CDCl3)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)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.
Example 18: (E) synthesis of (E) -1- (4-Fluorophenyl) -5-phenylpent-1-en-3-ol
The starting materials 1i (122mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod) were charged in this order into a reaction flask2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 24 hours. After the reaction, the mixture was filtered through celite, and the resulting filtrate was subjected to silica gel column chromatography with an eluent (ethyl acetate/petroleum ether: 1/10) to give 101mg of a colorless oily liquid in a yield of 79%.1H NMR(400MHz，CDCl3)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)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)，71.2，37.7，30.7.19FNMR(376MHz，CDCl3)F-114.0(s，ArF).HRMS(ESI)Calcd for[C17H16F，(M+H)-H2O]+：239.1231，Found：239.1223.
Example 19: (E) synthesis of (E) -1- (2-Fluorophenyl) -5-phenylpent-1-en-3-ol
The reaction flask was charged with the starting materials 1j (122mg, 1.0mmol), 2a (67mg, 0.5mmol), Ni (cod)2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 24 hours. After the reaction, the mixture was filtered through celite, and the resulting product was chromatographed on silica gel with an eluent (ethyl acetate/petroleum ether: 1/5) to give 91mg of a colorless oily liquid with a yield of 71%.1H NMR(400MHz，CDCl3)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)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)F-117.7(s，ArF).HRMS(ESI)Calcdfor[C17H16F，(M+H)-H2O]+：239.1231，Found：239.1236
Example 20: synthesis of Stirpentitol
The reaction flask was charged with the starting materials 5(148mg, 1.0mmol), 6(43mg, 0.5mmol), Ni (cod)2(13.8mg，0.05mmol)，PhB(OH)2(12.2mg, 0.1mmol), ethanol (2mL), 75 deg.C, under nitrogen for 24 hours. After the reaction, the mixture was filtered through celite, and the resulting filtrate was purified by silica gel column chromatography with an eluent (ethyl acetate/petroleum ether: 1/5) to give 59mg of a white solid with a yield of 50%.1H NMR(400MHz，CDCl3)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)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 (5)
1. The preparation method for synthesizing the E-allyl alcohol compound by one-step coupling of olefin and aldehyde is characterized by comprising the following steps:
sequentially adding raw materials 1 and 2, a phosphine ligand, arylboronic acid, a nickel catalyst and a solvent into a reaction bottle, stirring for 16 hours at a specified temperature in a nitrogen atmosphere, cooling to room temperature, removing the solvent under reduced pressure, and performing column chromatography separation to obtain a target product 3;
r in the raw material 1 and the product 31Is aryl; r in the raw material 2 and the product 32Is hydrogen, alkyl, aryl or heteroaryl; the phosphine ligand is one or more of tricyclopentyl phosphine and tricyclohexyl phosphine; the nickel catalyst is Ni (cod)2(ii) a The solvent is an alcohol solvent; the specified temperature is any of 25 ℃ to 75 ℃.
2. The method for preparing the compound of E-allyl alcohol by one-step coupling of olefin and aldehyde according to claim 1, wherein the nickel catalyst is Ni (cod)2The dosage of the catalyst is 5-20 mol% of the raw material 2.
3. The preparation method for synthesizing the E-allyl alcohol compound by one-step coupling of olefin and aldehyde according to claim 1, wherein the phosphine ligand is one or more of tricyclopentylphosphine and tricyclohexylphosphine, and the usage amount of the phosphine ligand is 15-40 mol% of the raw material 2.
4. The method for preparing the compound of E-allyl alcohol through one-step coupling of olefin and aldehyde according to claim 1, wherein the aryl boric acid is one or more of phenylboronic acid, pentafluorophenylboronic acid or 4-trifluoromethylphenylboronic acid, and the dosage of the aryl boric acid is 5-50 mol% of the raw material 2.
5. The method for preparing the compound of E-allyl alcohol through one-step coupling of olefin and aldehyde according to claim 1, wherein the alcohol solvent is one or more of methanol, ethanol or isopropanol, and the amount of the alcohol solvent is 5mL to 10mL for 2 mmol of raw material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060659A (en) * | 2010-11-12 | 2011-05-18 | 西北师范大学 | Method for preparing homoallylic alcohol |
| CN104788274A (en) * | 2015-03-30 | 2015-07-22 | 武汉理工大学 | Preparation method of chiral 1, 3-butadiene-2-secondary alcohol |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060659A (en) * | 2010-11-12 | 2011-05-18 | 西北师范大学 | Method for preparing homoallylic alcohol |
| CN104788274A (en) * | 2015-03-30 | 2015-07-22 | 武汉理工大学 | Preparation method of chiral 1, 3-butadiene-2-secondary alcohol |
Non-Patent Citations (2)
| Title |
|---|
| 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;郑彦龙等;《中国化学会第30届学术年会摘要集》;20160701;全文 * |
| 铁催化的非活化醛类和简单烯烃的选择性转移氢化偶联;叶萌春;《有机化学》;20160715;第1713页 * |
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