CN110317134A - A kind of cis--α, β-ethylenic unsaturation hydrocarbon compound preparation method - Google Patents
A kind of cis--α, β-ethylenic unsaturation hydrocarbon compound preparation method Download PDFInfo
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- CN110317134A CN110317134A CN201910649947.8A CN201910649947A CN110317134A CN 110317134 A CN110317134 A CN 110317134A CN 201910649947 A CN201910649947 A CN 201910649947A CN 110317134 A CN110317134 A CN 110317134A
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 11
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical class [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000007871 hydride transfer reaction Methods 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- -1 carbonium ion salt Chemical class 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 238000010189 synthetic method Methods 0.000 abstract description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 9
- 230000002194 synthesizing effect Effects 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 1
- QKLXBIHSGMPUQS-FGZHOGPDSA-M (3r,5r)-7-[4-(4-fluorophenyl)-2,5-dimethyl-1-phenylpyrrol-3-yl]-3,5-dihydroxyheptanoate Chemical compound CC1=C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)C(C=2C=CC(F)=CC=2)=C(C)N1C1=CC=CC=C1 QKLXBIHSGMPUQS-FGZHOGPDSA-M 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PSWDQTMAUUQILQ-UHFFFAOYSA-N 2-[(6-methoxy-4-methylquinazolin-2-yl)amino]-5,6-dimethyl-1h-pyrimidin-4-one Chemical compound N1=C(C)C2=CC(OC)=CC=C2N=C1NC1=NC(=O)C(C)=C(C)N1 PSWDQTMAUUQILQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940125796 compound 3d Drugs 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000201 insect hormone Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QAPTWHXHEYAIKG-RCOXNQKVSA-N n-[(1r,2s,5r)-5-(tert-butylamino)-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](NC(C)(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 QAPTWHXHEYAIKG-RCOXNQKVSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
Abstract
The invention discloses the cis--α of one kind for belonging to technical field of organic synthesis, β-ethylenic unsaturation hydrocarbon compound preparation methods.The method are as follows: in the presence of non-metal carbon cation salt, α-diazonium compound 1,2- Hydride transfer is reacted.Cis--α of the present invention, β-ethylenic unsaturation hydrocarbon compound synthetic method have it is scientific and reasonable, environmental-friendly, synthetic method is simple, and target compound yield is higher, and product is easy to the features such as purifying.
Description
Technical field
The invention discloses the cis--α of one kind for belonging to technical field of organic synthesis, the preparations of β-ethylenic unsaturation hydrocarbon compound
Method.
Background technique
α, β-unsaturated compound are widely present in natural products, such as: insect hormone, alkaloid etc..And α, β-insatiable hunger
With the important intermediate that compound is in organic synthesis, studies its synthesis and have a very important significance.However, compared to anti-
Formula-α, β-ethylenic unsaturation hydrocarbon compound, the synthetic method of cis-structure compound are relatively fewer.Currently, cis--α, β-are no
Saturation of olefins compound can by the reduction of unsaturated aldehydes based compound, or light irradiation under the conditions of realize to it is trans--no
The conversion of saturation of olefins compound.α-diazonium compound has been widely used in organic synthesis as a kind of important source material.
In fact, metal Rh (II) can realize the reaction of α-benzyl diazotate 1,2- Hydride transfer by metal carbene intermediate,
And Z- α is obtained, beta-unsaturated acid ester, however the type compound is normally only to occur as a kind of by-product.Due to current
The limitation for synthesizing such compound method, finds that a kind of environmental-friendly, structure is simple and efficient catalytic synthesizing cis-α, β-
The method of ethylenic unsaturation hydrocarbon compound is just particularly important.
Summary of the invention
The purpose of the invention is to overcome existing synthesizing cis-α, existing for β-ethylenic unsaturation hydrocarbon compound method
Using noble metal catalyst, cis-selective is lower the defects of, provide a kind of nonmetal catalyzed cis--α, β-ethylenic unsaturation
The preparation method of hydrocarbon compound.
To achieve the goals above, the present invention provides cis--α shown in a kind of synthesis formula (I), β ethylenic unsaturation hydrocarbonylations
The preparation method of object is closed, this method comprises: in the presence of non-metal carbon cation salt, by α-diazo compounds shown in formula (II)
1, the 2- Hydride transfer of object reacts.
Wherein, R1For alkyl, substituted or unsubstituted C6-C20 selected from substituted or unsubstituted C1-C10 aryl and
One of substituted or unsubstituted heterocyclic group；EWG be ester group, cyano, substituted or unsubstituted C6-C20 aromatic carbonyl and
One of substituted or unsubstituted C1-C10 alkyl carbonyl.
Preferably, α-diazonium compound of opposite 100 molar parts, the dosage of non-metal carbon cation salt are rubbed for 0.5-10
That part, more preferably 1-5 molar part.
Preferably, the non-metal carbon cation salt is at least one of tri-aryl compounds shown in formula (III),
Wherein, Ar be substituted or unsubstituted C6-C20 one of aryl, Y be halogen, tetrafluoro boric acid, perchloric acid,
One of hexafluorophosphoric acid, hexafluoro-antimonic acid, trifluoromethanesulfonic acid or four (3,5- bis- (trifluoromethyl) phenyl) acid anions.
Preferably, the reaction of α-diazonium compound 1,2- Hydride transfer 25-60 DEG C at a temperature of, reaction stirring 1-60 point
Clock.
Preferably, column chromatography is carried out with the mixed solvent of petroleum ether and ethyl acetate after the reaction.
The method of synthesizing cis-α of the present invention, β ethylenic unsaturation hydrocarbon compound has following compared with present technology
Advantage:
(1) catalyst used in is non-metal carbon cation salt catalyst, and structure is simple and environmental-friendly, synthetic method
Simply, easily operated；
(2) synthetic method used catalyst has high catalytic efficiency, high-cis selectivity；
(3) cis--α that the present invention synthesizes, β ethylenic unsaturation hydrocarbon compound warp1HNMR、13CNMR is accredited as pure target and produces
Object；
(4) method of the present invention is easy to be mass produced, and the cis-selective of yield can be protected after amplification
It holds.
Detailed description of the invention
Fig. 1 is the NMR spectra of compound 3a prepared by embodiment 1；
Fig. 2 is the NMR spectra of compound 3b prepared by embodiment 2；
Fig. 3 is the NMR spectra of compound 3c prepared by embodiment 3；
Fig. 4 is the NMR spectra of compound 3d prepared by embodiment 4.
Specific embodiment
Method of the invention is illustrated herein by specific embodiment, but the present invention is not limited thereto at this
In the range of the technology design of invention, any modifications, equivalent substitutions and improvements etc. are carried out, should all include in protection model of the invention
Within enclosing.
The method of synthesizing cis-α of the present invention, β ethylenic unsaturation hydrocarbon compound includes: in non-metal carbon cation salt
In the presence of, α-diazonium compound 1,2- Hydride transfer is reacted.
In the present invention, shown in the structure such as formula (II) of the α-diazonium compound.
In formula (II), R1For alkyl, alkenyl, substituted or unsubstituted C6- selected from substituted or unsubstituted C1-C10
One of the aryl of C20 and substituted or unsubstituted heterocyclic group, wherein " substituted or unsubstituted " is only to be taken with substituent group
Generation or unsubstituted corresponding group；The substituent group refers to the alkyl of halogenated (such as: fluorine, chlorine, bromine) or C1-C4 (such as: methyl, second
Base, propyl, butyl)；The alkyl of C1-C10 specifically for example can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, penta
Base, isopentyl, hexyl, isohesyl, heptyl, different heptyl, octyl, iso-octyl, nonyl etc., in a specific embodiment, institute
Stating groups is nonyl；The alkenyl of C2-C10 specifically for example can be vinyl, acrylic, cyclobutenyl, isobutenyl, styrene
Base etc., in a specific embodiment, the groups are alkenyl；The aryl of C6-C20 can be for example specifically phenyl, connection
Hydrogen in phenyl, naphthalene and these groups is by one or more (such as 2-8) alkyl-substituted groups；The heterocyclic group
In hetero atom for example can be sulphur, oxygen or nitrogen, preferably oxygen, in a specific embodiment, the heterocyclic group are furan
It mutters base.
In formula (II), EWG is ester group and cyano, the aromatic carbonyl of substituted or unsubstituted C6-C20 and substituted or unsubstituted
One of C1-C10 alkyl carbonyl；The ester group can be R4- O-CO-, wherein R4For the alkyl of C1-C4, preferably second
Base；In a specific embodiment, the ester is Et-O-CO-.
In method of the present invention, α-diazonium compound of opposite 100 molar parts, the use of non-metal carbon cation salt
Amount is 0.5-10 molar part, more preferably 1-5 molar part, most preferably 5 molar parts.
In method of the present invention, the non-metal carbon cation salt be shown in formula (III) in compound at least
One kind,
Wherein, Ar be substituted or unsubstituted C6-C20 aryl, Y be halogen, tetrafluoro boric acid, perchloric acid, hexafluorophosphoric acid,
One of hexafluoro-antimonic acid, trifluoromethanesulfonic acid or four (3,5- bis- (trifluoromethyl) phenyl) acid anions, it is " substituted or unsubstituted
" refer to the substituted or unsubstituted corresponding group of substituent group substituent group；The substituent group refer to halogen (such as: fluorine, chlorine, bromine) or
The alkyl (such as methyl, ethyl, propyl, butyl) of C1-C4；The aryl of C6-C20 specifically for example can for phenyl, xenyl and
By one or more (such as 2-8) alkyl-substituted groups in these groups.
In method of the present invention, it is preferable that 1, the 2- Hydride transfer of the α-diazonium compound is reacted in 25-60
At a temperature of DEG C, stirring is carried out 1-60 minutes.
In method of the present invention, in order to obtain pure target product, the method it is also preferable to include: after the reaction
Column chromatography is carried out with the mixed solution of petroleum ether and ethyl acetate；In the in the mixed solvent of petroleum ether and ethyl acetate, petroleum ether
Volume ratio with ethyl acetate can be 5-50:1, preferably 10-40:1, most preferably 20:1.
In a specific embodiment, the synthesizing cis-α, β-ethylenic unsaturation hydrocarbon compound method includes:
(1) reaction is added according to the amount of α-diazonium compound 0.5-10mol% in non-metal carbon cation salt catalyst
Device, wherein the reaction dissolvent is in methylene chloride, chloroform, 1,2- dichloroethanes, benzene, toluene, n-hexane and acetonitrile
It is at least one；
(2) α-diazonium compound is added to the reactor of (1)；
(3) under conditions of 25-60 DEG C, reaction stirring purified target product after 1-60 minutes.
Present invention is further described in detail by the following examples:
Embodiment 1
Reaction equation is as follows:
Catalyst 1a (5mmol) is added in reactor, methylene chloride 500mL is added, compound 2a is then added
(100mmol), is stirred at room temperature, and 60min reaction is completed, with the mixing of petroleum ether and the volume ratio 20:1 of ethyl acetate
Solvent column chromatography, obtains pure 3a.The yield of 3a is that 84%, Z/E is selectively 94:6.
3a nuclear magnetic data is as follows:
1H NMR(500MHz,CDCl3): δ 7.57 (d, J=7.0Hz, 2H), 7.36-7.31 (m, 3H), 6.93 (d, J=
13.0Hz, 1H), 5.94 (d, J=12.5Hz, 1H), 4.17 (q, J=7.0Hz, 2H), 1.23 (t, J=7.5Hz, 3H) ppm.
13C NMR(125MHz,CDCl3):δ166.2,143.0,134.8,129.7,128.9,128.0, 119.9,
60.3,14.1ppm.
Embodiment 2
Reaction equation is as follows:
Catalyst 1b (5mmol) is added in reactor, methylene chloride 500mL is added, compound 2b is then added
(100mmol), is stirred at room temperature, and 60min reaction is completed, with the mixing of petroleum ether and the volume ratio 20:1 of ethyl acetate
Solvent column chromatography, obtains pure 3b.The yield of 3b is that 83%, Z/E is selectively 99:1.
3b nuclear magnetic data is as follows:
1H NMR(500MHz,CDCl3):δ8.13(s,1H),7.38-7.31(m,6H),6.93(s,1 H),6.73(d,J
=12.5Hz, 1H), 5.85 (d, J=12.5Hz, 1H), 5.20 (s, 2H) ppm.
13C NMR(125MHz,CDCl3):δ165.9,147.1,142.9,136.0,134.3,128.5, 128.2,
121.2,116.2,112.2,65.9ppm.
Embodiment 3
Reaction equation is as follows:
Catalyst 1c (5mmol) is added in reactor, methylene chloride 500mL is added, compound 2c is then added
(100mmol), is stirred at room temperature, and 60min reaction is completed, with the mixing of petroleum ether and the volume ratio 20:1 of ethyl acetate
Solvent column chromatography, obtains pure 3c.The yield of 3c is that 51%, Z/E is selectively 99:1.
3c nuclear magnetic data is as follows:
1H NMR(500MHz,CDCl3): δ 7.37-7.31 (m, 2H), 6.28-6.22 (m, 1H), 5.81 (d, J=
11.5Hz,1H),5.15(s,2H),2.68-2.64(m,2H),1.44-1.40(m,2H),1.28-1.26 (m,12H),0.88
(t, J=6.5Hz, 3H) ppm；
13C NMR(125MHz,CDCl3):δ166.2,151.4,136.2,128.5,128.1,128.1, 119.2,
65.6,31.9,29.7,29.5,29.4,29.3,29.1,29.0,22.6,14.1ppm.
Embodiment 4
Reaction equation is as follows:
Catalyst 1d (5mmol) is added in reactor, methylene chloride 500mL is added, compound 2d is then added
(100mmol), is stirred at room temperature, and 60min reaction is completed, with the mixing of petroleum ether and the volume ratio 20:1 of ethyl acetate
Solvent column chromatography, obtains pure 3d.The yield of 3d is that 39%, Z/E is selectively 99:1.
3d nuclear magnetic data is as follows:
1H NMR(500MHz,CDCl3): δ 7.67-7.60 (m, 1H), 7.38-7.31 (m, 5H), 6.59 (t, J=
11.0Hz, 1H), 5.75 (d, J=11.5Hz, 1H), 5.56-5.51 (m, 2H), 5.18 (s, 2H) ppm.
13C NMR(125MHz,CDCl3):δ165.8,145.4,136.0,132.9,128.5,128.2, 126.3,
118.1,65.9ppm.
There is examples detailed above to can be seen that according to synthesizing cis-α of the present invention, β-ethylenic unsaturation hydrocarbon compound side
Method can obtain the target product of higher yield and Z- selectivity.
Claims (5)
1. cis--α shown in a kind of synthesis formula (I), β-ethylenic unsaturation hydrocarbon compound preparation method, this method comprises: non-
In the presence of metal carbonium ion salt, α-diazonium compound 1,2- Hydride transfer shown in formula (II) is reacted,
Wherein, R1For the aryl of alkyl, substituted or unsubstituted C6-C20 selected from substituted or unsubstituted C1-C10 and substitution or
One of unsubstituted heterocyclic group；EWG be ester group, cyano, the aromatic carbonyl of substituted or unsubstituted C6-C20 and substitution or
One of unsubstituted C1-C10 alkyl carbonyl.
2. preparation method according to claim 1, wherein relative to the α-diazonium compound of 100 molar parts, non-gold
The dosage for belonging to carbonium ion salt is 0.5-10 molar part.
3. preparation method according to claim 1, wherein the non-metal carbon cation is three virtue shown in formula (III)
Base carbonium ion salt compound,
Wherein, Ar is one of the aryl of substituted or unsubstituted C6-C20, and Y is chlorine, bromine, tetrafluoro boric acid, hexafluorophosphoric acid, six
One of fluorine metaantimmonic acid, trifluoromethanesulfonic acid or four (3,5- bis- (trifluoromethyl) phenyl) acid anions.
4. preparation method according to claim 1, wherein 1, the 2- Hydride transfer reaction of the α-diazonium compound exists
At a temperature of 25-60 DEG C, reaction stirring is carried out 1-60 minutes.
5. preparation method according to claim 1, wherein after the reaction with the mixed solvent of petroleum ether and ethyl acetate into
Row column chromatography.
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| CN111217742A (en) * | 2019-11-21 | 2020-06-02 | 青岛科技大学 | Method for asymmetrically constructing C-S and C-O bond dual-functionalization by one-pot method |
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2019
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| MANUEL TORRE等: "The intermediate formation of ketocarbenes and the conformational control in the Wolff rearrangement of a-diazoketones", 《CAN. J. CHEM.》 * |
| STEPHAN BACHMANN等: "Cu(I)-carbenoid- and Ag(I)-Lewis acid-catalyzed asymmetric intermolecular insertion of a-diazo compounds into N–H bonds", 《ORG.BIOMOL.CHEM.》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111217742A (en) * | 2019-11-21 | 2020-06-02 | 青岛科技大学 | Method for asymmetrically constructing C-S and C-O bond dual-functionalization by one-pot method |
| CN111217742B (en) * | 2019-11-21 | 2023-02-21 | 青岛科技大学 | Method for asymmetrically constructing double functionalization of C-S and C-O bonds by one-pot method |
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