CN115838330A - Method for synthesizing dicarboxylic acid compounds based on remote carboxylation of non-activated olefin - Google Patents
Method for synthesizing dicarboxylic acid compounds based on remote carboxylation of non-activated olefin Download PDFInfo
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- CN115838330A CN115838330A CN202111106015.2A CN202111106015A CN115838330A CN 115838330 A CN115838330 A CN 115838330A CN 202111106015 A CN202111106015 A CN 202111106015A CN 115838330 A CN115838330 A CN 115838330A
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- carboxylation
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 40
- 238000006473 carboxylation reaction Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000021523 carboxylation Effects 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 title description 2
- -1 dicarboxylic acid compound Chemical class 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 23
- 239000011941 photocatalyst Substances 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 51
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 34
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 30
- 125000001072 heteroaryl group Chemical group 0.000 claims description 30
- 150000002431 hydrogen Chemical class 0.000 claims description 30
- 125000003342 alkenyl group Chemical group 0.000 claims description 27
- 125000000304 alkynyl group Chemical group 0.000 claims description 27
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 150000001408 amides Chemical class 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 15
- 125000003368 amide group Chemical group 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 11
- 125000004185 ester group Chemical group 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000004423 acyloxy group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000004104 aryloxy group Chemical group 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000012973 diazabicyclooctane Substances 0.000 claims description 3
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000004673 fluoride salts Chemical class 0.000 claims description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims 3
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 claims 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- 125000005587 carbonate group Chemical group 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 21
- 239000000047 product Substances 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 44
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 20
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 20
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 20
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 20
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- CPPKAGUPTKIMNP-UHFFFAOYSA-N cyanogen fluoride Chemical compound FC#N CPPKAGUPTKIMNP-UHFFFAOYSA-N 0.000 description 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- XRKQMIFKHDXFNQ-UHFFFAOYSA-N n-cyclohexyl-n-ethylcyclohexanamine Chemical compound C1CCCCC1N(CC)C1CCCCC1 XRKQMIFKHDXFNQ-UHFFFAOYSA-N 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 5
- ZWVMLYRJXORSEP-LURJTMIESA-N (2s)-hexane-1,2,6-triol Chemical compound OCCCC[C@H](O)CO ZWVMLYRJXORSEP-LURJTMIESA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VYKNVAHOUNIVTQ-UHFFFAOYSA-N 1,2,2,3,3-pentamethylpiperidine Chemical compound CN1CCCC(C)(C)C1(C)C VYKNVAHOUNIVTQ-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- GCGRXVMGBHYMDA-UHFFFAOYSA-N 5-fluoro-2,4,6-tris(N-phenylanilino)benzene-1,3-dicarbonitrile Chemical compound C1(=CC=CC=C1)N(C1=C(C#N)C(=C(C(=C1C#N)N(C1=CC=CC=C1)C1=CC=CC=C1)F)N(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 GCGRXVMGBHYMDA-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
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- 238000013508 migration Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229930192474 thiophene Chemical group 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 description 1
- ZOMQCVKHGOMNER-UHFFFAOYSA-N 2,4,5,6-tetrakis(N-phenylanilino)benzene-1,3-dicarbonitrile Chemical compound C(#N)C1=C(C(=C(C(=C1N(C1=CC=CC=C1)C1=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1)C#N)N(C1=CC=CC=C1)C1=CC=CC=C1 ZOMQCVKHGOMNER-UHFFFAOYSA-N 0.000 description 1
- QMXFUIUEGUOSEV-UHFFFAOYSA-N 3,4,5,6-tetra(carbazol-9-yl)benzene-1,2-dicarbonitrile Chemical compound N#Cc1c(C#N)c(c(c(c1-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12 QMXFUIUEGUOSEV-UHFFFAOYSA-N 0.000 description 1
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- INVGTCJGWUABRZ-UHFFFAOYSA-N 3,4,5,6-tetrakis(3,6-ditert-butylcarbazol-9-yl)benzene-1,2-dicarbonitrile Chemical compound C(C)(C)(C)C=1C=CC=2N(C3=CC=C(C=C3C=2C=1)C(C)(C)C)C1=C(C(C#N)=C(C(=C1N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C(C)(C)C)C(C)(C)C)N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C(C)(C)C)C(C)(C)C)N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C(C)(C)C)C(C)(C)C)C#N INVGTCJGWUABRZ-UHFFFAOYSA-N 0.000 description 1
- VPCXVCNTHAMRBT-UHFFFAOYSA-N 3,5-difluoro-2,4,6-tris(n-phenylanilino)benzonitrile Chemical compound FC1=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C(C#N)=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C(F)=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 VPCXVCNTHAMRBT-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- ORNBQBCIOKFOEO-YQUGOWONSA-N Pregnenolone Natural products O=C(C)[C@@H]1[C@@]2(C)[C@H]([C@H]3[C@@H]([C@]4(C)C(=CC3)C[C@@H](O)CC4)CC2)CC1 ORNBQBCIOKFOEO-YQUGOWONSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical class CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000003939 benzylamines Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing dicarboxylic acid compounds based on remote carboxylation of non-activated olefin, belonging to the technical field of organic synthesis and mainly comprising the following steps: the olefinic compound, the photocatalyst and the base are added to a reaction vessel and then reacted in CO 2 Adding a reducing agent and a solvent in the atmosphere, stirring and reacting for 0.1-100 h at room temperature under the irradiation of visible light, and separating and purifying a reaction product to prepare a dicarboxylic acid compound; the preparation method of the invention has excellent reactivity for the non-activated olefin substrate, realizes the remote carboxylation reaction of the non-activated olefin at room temperature, and has the characteristics of convenient operation, cheap and easily obtained raw materials, mild reaction conditions, wide substrate universality and high product yield.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing dicarboxylic acid compounds based on remote carboxylation of non-activated olefin.
Background
The wide existence of olefin compounds has made them play a very important role in organic synthetic chemistry, and a wide variety of compounds can be synthesized by functionalizing an olefin double bond, and have been widely used in the fields of pharmaceutical chemistry, polymer chemistry, material chemistry, and the like.
In recent years, with the efforts of chemists, the bifunctional of activated olefins has been greatly advanced and has become an effective means for efficiently constructing complex compound molecules, but the bifunctional of non-activated olefins still faces a great challenge. Due to non-activated olefins and CO 2 The chemical inertness of (a) makes the research on the double carboxylation reaction of non-activated olefin fresh, so that the synthesis of dicarboxylic acids with different chain lengths faces a greater challenge. On the other hand, carbon dioxide is an excellent carbon-carbon with wide source, low price, easy availability and reproducibilitySynthons are widely used in various chemical syntheses. Therefore, it is very significant to provide a method for synthesizing dicarboxylic acid compounds by remote carboxylation of non-activated olefins using carbon dioxide.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a method for synthesizing dicarboxylic acid compounds based on remote carboxylation of non-activated olefin, which can effectively solve the problem of blank research on remote double carboxylation reaction of non-activated olefin by using carbon dioxide in the prior art, and has the characteristics of convenient operation, cheap and easily available raw materials, mild reaction conditions, wide substrate universality and high product yield.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for synthesizing dicarboxylic acid compounds based on remote carboxylation of non-activated olefin, which comprises the following steps:
the olefinic compound, the photocatalyst and the base are added to a reaction vessel and then reacted in CO 2 Adding a reducing agent and a solvent in the atmosphere, stirring and reacting for 0.1-100 h at room temperature under the irradiation of visible light, and separating and purifying a reaction product to prepare a dicarboxylic acid compound; wherein, the mol ratio of the olefin compound, the photocatalyst, the alkali and the reducing agent is 1 (0.001-0.5) to (0.1-10) to (1-10);
the structural general formula of the olefin compound is as follows:
wherein R is 1 Hydrogen, ester group, carboxyl group, amide group, cyano group, aryl group, heteroaryl group, alkynyl group, alkenyl group or alkyl group (the alkyl group includes methyl group, ethyl group, isopropyl group, tert-butyl group, hydroxymethyl group, acetoxymethyl group, trifluoromethyl group, etc.); r 2 Is hydrogen, ester group, carboxyl group, amido group, cyano group, aryl group, heteroaryl group, alkynyl group, alkenyl group or alkyl group (the alkyl group comprises methyl, ethyl, isopropyl, tert-butyl, hydroxymethyl, acetoxymethyl and trifluoromethylEtc.); r 3 Hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 4 Hydrogen, aryl, heteroaryl, ester, carboxyl, amide, cyano, fluorine, chlorine, bromine, iodine, boron, silicon, phosphine, thioether, alkoxy, acyloxy, aryloxy, amine, alkynyl, alkenyl, or alkyl (alkyl including methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 5 Hydrogen, methoxycarbonyl, ethoxycarbonyl or tert-butoxycarbonyl or alkyl (including methyl, ethyl, isopropyl, tert-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 6 Hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 7 Hydrogen, aryl, heteroaryl, ester, carboxyl, amide, cyano, fluorine, chlorine, bromine, iodine, boron, silicon, phosphine, thioether, alkoxy, acyloxy, aryloxy, amine, alkynyl, alkenyl or alkyl (alkyl including methyl, ethyl, isopropyl, tert-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 8 Hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 9 Hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 10 Hydrogen, aryl, heteroaryl, ester, carboxyl, amide, cyano, fluorine, chlorine, bromine, iodine, boron, silicon, phosphine, thioether, alkoxy, acyloxy, aryloxy, amine, alkynyl, alkenyl or alkyl (alkyl including methyl, ethyl, isopropyl, tert-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 11 Is hydrogen or alkyl; n is 1 or 2 or3; the dotted ring is an aromatic or heteroaromatic ring (e.g., a pyridine ring, furan ring or thiophene ring), preferably a benzene ring.
Furthermore, the mol ratio of the olefin compound, the photocatalyst, the alkali and the reducing agent is 1 (0.005-0.1): 4.5-6.5): 2.5.
Further, the structural formula of the olefin compound is as follows:
further, the photocatalyst is a D-A type photocatalyst or an Ir photocatalyst.
Further, the photocatalyst is 4CzIPN, 4DPAIPN, 3DPAFIPN, 3DPA2FBN, 5CzBN, 4CzPN, DPZ, 4CzPN-Ph, 4CzPN-Bu, 4CzTPN-Bu, ir (dFCF) 3 ppy) 2 (dtbbpy)PF 6 、fac-Ir(dF(ppy) 3 )、fac-Ir(ppy) 3 And Ir (ppy) 2 (dtbbpy)PF 6 At least one of them.
Further, the carbonate of the alkali is Cs 2 CO 3 、K 2 CO 3 、Na 2 CO 3 Or Li 2 CO 3 (ii) a The bicarbonate is CsHCO 3 、KHCO 3 Or NaHCO 3 (ii) a The fluoride salt is CsF or KF; the tert-butoxide salt is KO t Bu、NaO t Bu or LiO t Bu; the phosphate is K 3 PO 4 Or Na 3 PO 4 (ii) a The carboxylate is CsOAc, KOAc, naOAc, csOPiv or KOPiv; the organic base is DBU, TBD, DABCO, TMG or DBN.
Further, the organic amine compound as the reducing agent is Cy 2 NEt、Cy 2 NMe、 i Pr 2 NEt、NEt 3 Or PMP (pentamethylpiperidine).
Further, the wavelength of visible light is 400 to 560nm, and the power of visible light is 3 to 60W, preferably 20 to 30W.
Further, the pressure of carbon dioxide is 0.5 to 30 times atmospheric pressure, preferably 1 to 5 times atmospheric pressure.
Further, the solvent concentration is 0.01 to 10.0M, and the solvent is preferably DMSO, NMP, DMF, DMAc, THF, DCM, meOH, meCN or the like.
Furthermore, the reaction time is 2-60 h.
The reaction formula of the invention is as follows:
wherein R is 1 Hydrogen, ester group, carboxyl group, amide group, cyano group, aryl group, heteroaryl group, alkynyl group, alkenyl group or alkyl group (the alkyl group includes methyl group, ethyl group, isopropyl group, tert-butyl group, hydroxymethyl group, acetoxymethyl group, trifluoromethyl group, etc.); r 2 Hydrogen, ester group, carboxyl group, amide group, cyano group, aryl group, heteroaryl group, alkynyl group, alkenyl group or alkyl group (the alkyl group includes methyl group, ethyl group, isopropyl group, tert-butyl group, hydroxymethyl group, acetoxymethyl group, trifluoromethyl group, etc.); r 3 Is hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 4 Hydrogen, aryl, heteroaryl, ester, carboxyl, amide, cyano, fluorine, chlorine, bromine, iodine, boron, silicon, phosphine, thioether, alkoxy, acyloxy, aryloxy, amine, alkynyl, alkenyl, or alkyl (alkyl including methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 5 Hydrogen, methoxycarbonyl, ethoxycarbonyl or tert-butoxycarbonyl or alkyl (including methyl, ethyl, isopropyl, tert-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 6 Hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 7 Is hydrogen, aryl, heteroaryl, ester group,Carboxyl, amide, cyano, fluorine, chlorine, bromine, iodine, boron, silicon, phosphine, sulfide, alkoxy, acyloxy, aryloxy, amine, alkynyl, alkenyl, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 8 Hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 9 Hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 10 Hydrogen, aryl, heteroaryl, ester, carboxyl, amide, cyano, fluorine, chlorine, bromine, iodine, boron, silicon, phosphine, thioether, alkoxy, acyloxy, aryloxy, amine, alkynyl, alkenyl or alkyl (alkyl including methyl, ethyl, isopropyl, tert-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 11 Is hydrogen or alkyl; n is 1 or 2 or 3; the dotted ring is an aromatic or heteroaromatic ring (e.g., a pyridine ring, furan ring or thiophene ring), preferably a benzene ring.
The reaction mechanism of the invention is shown in figure 1, and the specific process is as follows: with Ir III A catalyst is taken as an example; first, light-excited Ir III Catalyst formation [ Ir III ] * Species, further under the action of light, reducing carbon dioxide to carbon dioxide radical anions and Ir IV Species, ir IV The species is reduced to Ir by the electron reductant III A species; carrying out free radical addition on olefin by the formed carbon dioxide free radical negative ion to generate an alkyl carbon free radical intermediate (I); then intramolecular 1, n-hydrogen migration is carried out to generate a more stable benzyl free radical (II); the benzyl free radical (II) is further reduced to generate a benzyl carbanion intermediate; finally attacking carbon dioxide and acidifying to obtain the target dicarboxylic acid derivative.
In summary, the invention has the following advantages:
1. the invention provides a method for synthesizing dicarboxylic acid compounds based on remote carboxylation of non-activated olefin, which comprises the steps of under the catalysis of visible light, taking the non-activated olefin compound as a reaction substrate, taking carbon dioxide as a carboxylic acid source, and simultaneously adding a photocatalyst, a reducing agent and alkali to prepare the dicarboxylic acid compounds; the method has the characteristics of convenient operation and cheap and easily obtained raw materials;
2. the preparation method disclosed by the invention has excellent reactivity on the non-activated olefin substrate, realizes the remote carboxylation reaction of the non-activated olefin at room temperature, and has the characteristics of mild reaction conditions, wide substrate universality and high product yield.
Drawings
FIG. 1 is a diagram showing the reaction mechanism in the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a method for synthesizing dicarboxylic acid compounds based on remote carboxylation of non-activated olefin, which comprises the following specific steps:
after drying a 25mL Schlenk reaction tube equipped with a stirrer under vacuum, 0.2mmol of non-activated olefin (added at this time if the reaction substrate is a solid; added via syringe in the previous step of solvent addition if the reaction substrate is a liquid) and photocatalyst fac-Ir (ppy) were added 3 (1 mol%), followed by placing in a glove box and adding 4.5 equivalents Cs 2 CO 3 Rear sealTaking the tube out of the glove box in CO 2 Extracting the replacement gas three times under the double-row pipe of the atmosphere, and after the extraction and the replacement are finished, in CO 2 2.5 equivalents of DCyEA (dicyclohexylethylamine) and 2mL of DMSO were added under a gas stream; after the solvent is added, the tube is sealed and placed at a position 1cm away from 30W blue LEDs, the mixture is stirred for 48 hours at room temperature, after the reaction is finished, 3mL of 2N HCl and 3mL of ethyl acetate are added, the mixture is stirred for 5 minutes, then 15mL of water is added, the mixture is extracted for 6 times by ethyl acetate, organic phases are combined, and the organic phases are spin-dried on a rotary evaporator; the solid residue is separated by a silica gel column to obtain the target product 2 of the dicarboxylated derivative. The specific results are as follows:
note: the above results are all separation results, and the bracket is used for recovering raw materials; [ a ] A]Representing 4 millimolar scale with a reaction time of 94h; [ b ] a]Is represented by using 6.5 equivalents of Cs 2 CO 3 ；[c]Expressed as using 5.5 equivalents of Cs 2 CO 3 ；[d]Represented by passing TMSCH 2 N 2 Carrying out esterification; [ e ]]Representative is complete conversion of substrate.
The experimental results show that the long-chain olefin substrate modified by different substituents can be compatible with electron-rich groups, electron-poor groups and charge neutral groups, and the target double-carboxylation product can be obtained with moderate yield. A variety of functional groups or substituents are compatible in the reaction system, including: fluorine, methyl methoxy, phenyl, carboxyl and amido. In addition, the system is compatible with long-chain alkenes derived from dibenzopyran, olefins substituted by monoaryl and the like, and has good reaction effect.
Example 2
The embodiment provides a method for synthesizing dicarboxylic acid compounds based on remote carboxylation of non-activated olefin, which comprises the following specific steps:
will be provided with a stirrerAfter drying the 25mL Schlenk tube under vacuum, 0.2mmol of non-activated olefin (added at this time if the reaction substrate is a solid; added via syringe in the previous step of solvent addition if the reaction substrate is a liquid) and the photocatalyst fac-Ir (ppy) were added 3 (0.5 mol%), followed by placing in a glove box and adding 5 equivalents Cs 2 CO 3 Taking the rear sealed tube out of the glove box in CO 2 Extracting the replacement gas three times under the atmosphere of double-calandria, and after the extraction and replacement are finished, extracting CO 2 2.5 equivalents of DCyEA and 2mL of DMSO were added under air flow; after the solvent is added, placing the reaction solution at a position 1cm away from 30W blue LEDs, stirring at room temperature for 48h, after the reaction is finished, adding 3mL of 2N HCl and 3mL of ethyl acetate, stirring for 5min, then adding 15mL of water, extracting for 6 times by using ethyl acetate, combining organic phases, and spin-drying on a rotary evaporator; and separating the solid residue by a silica gel column to obtain the target carboxylic acid product 5 or 6. The specific results are as follows:
note: the above results are all separation results, and the bracket is used for recovering raw materials; [ a ] A]Typically by post-acidification column separation; [ b ] a]Representative is fac-Ir (ppy) 3 (1mol％)；[c]Representative is fac-Ir (ppy) 3 (1mol％),Cs 2 CO 3 (4.5 equiv.).
The above experimental results show that the reaction of the present invention is compatible with many common functional groups, such as: carboxyl, ester, amide and cyano groups, to give the corresponding biscarboxylation products in moderate to upward yields. In addition, natural product derived substrates such as pregnenolone, menthol, also give the desired product in moderate yields. The corresponding target products can also be obtained for flexible olefins when no bridging group is present in the substrate. Notably, when the radical after migration is alpha to the amine group, it is possible to construct a remote carboxyl group-containing alpha-amino acid derivative.
Example 3
The embodiment provides a method for synthesizing dicarboxylic acid compounds based on remote carboxylation of non-activated olefin, which comprises the following specific steps:
after drying a 25mL Schlenk reaction tube equipped with a stirrer under vacuum, 0.2mmol of non-activated olefin (added at this time if the reaction substrate is a solid; added via syringe in the previous step of solvent addition if the reaction substrate is a liquid) and photocatalyst fac-Ir (ppy) were added 3 (1 mol%) was placed in a glove box, and 4.5 equivalent Cs was added 2 CO 3 Taking the back sealed tube out of the glove box in CO 2 Extracting the replacement gas three times under the atmosphere of double-calandria, and after the extraction and replacement are finished, extracting CO 2 2.5 equivalents of DCyEA and 2mL of DMSO were added under air flow; after the solvent is added, the tube is sealed and placed at a position 1cm away from 30W blue LEDs, the mixture is stirred for 48 hours at room temperature, after the reaction is finished, 3mL of 2N HCl and 3mL of ethyl acetate are added, the mixture is stirred for 5 minutes, then 15mL of water is added, the mixture is extracted for 6 times by ethyl acetate, organic phases are combined, and the organic phases are spin-dried on a rotary evaporator; and separating the solid residue by a silica gel column to obtain the target product 9 or 10 of the dicarboxylated derivative. The specific results are as follows:
note: the above results are all separation results, and the bracket is used for recovering raw materials; [ a ] A]Represented by Cs 2 CO 3 (5.5 equivalents); [ b ] a]Is represented by 1 HNMR assay 9 l; [ c ] A]Representative is fac-Ir (ppy) 3 (1mol％)Cs 2 CO 3 (5 equivalents).
The above experimental results show that: when benzylamine derivatives containing non-activated olefins are selected as substrates, a series of functionalized alpha amino acid derivatives can be obtained. The reaction can be compatible with electron-donating groups, electron-neutral groups and electron-withdrawing groups, and can be compatible with various common functional groups, such as halogen fluorine atoms, carboxyl groups, ester groups, amide groups, methoxyl groups, phenoxy groups and the like. It is to be noted that the reaction is compatible with substrates containing chlorine atoms, but also with the presence of small amounts of dechlorinated products, presumably due to the formation of CO 2 - Direct reduction of the C-Cl bond. In addition, the reaction is hindered by the positionAt a lower level, the ortho-substituted groups all gave the corresponding target products in moderate yields. The reaction is also compatible with disubstituted substrates and allows the construction of all carbon alpha amino acids. For disubstituted olefins, moderate yields of the desired product are obtained with good selectivity, although the conversion is not high. It is also of interest to obtain the biscarboxylated product in good yield for substrates not containing amino substitutions.
Example 4
In this example, diethyl 2-allyl-2- (3, 3-diphenylpropyl) malonate was used as a substrate for the reaction, and the influence on the reaction yield was examined by changing the reaction conditions. The specific process is as follows:
note: the above-mentioned intermediate yields and conversions are nuclear magnetic yields with DMAP as an internal standard and isolated yields in parentheses. PC1= Ir (ppy) 2 (dtbbpy)PF 6 ，PC2＝3DPAFIPN。
From the experimental results, the nuclear magnetic yield of the corresponding carboxylic acid under the reaction conditions of the invention is up to 82%, and a series of control experiments show that the iridium photocatalyst, the alkali, the reducing agent, the light and the carbon dioxide are indispensable and any one is lacked, so that the target product cannot be obtained. DMSO, cs 2 CO 3 DCyEA has obvious promotion effect on the reaction. When other photocatalysts, solvents, bases or reducing agents are used, the yield drops significantly.
The product prepared by the invention is subjected to nuclear magnetic resonance and mass spectrum characterization analysis, and the nuclear magnetic and mass spectrum characterization data result is consistent with the obtained product. The specific characterization data are as follows:
5, 5-bis (ethoxycarbonyl) -2, 2-diphenylazelaic acid
5, 5-bis (methoxycarbonyl) -2, 2-diphenylazelaic acid
5, 5-bis (tert-butyloxycarbonyl) -2, 2-diphenylazelaic acid
5, 5-bis (acetoxymethyl) -2, 2-diphenylazelaic acid
5, 5-bis (hydroxymethyl) -2, 2-diphenylazelaic acid
5- (ethoxycarbonyl) -2, 5-triphenylazelaic acid
2- ([ 1,1' -biphenyl ] -4-yl) -5, 5-bis (ethoxycarbonyl) -2-phenylazelaic acid
2- (4-carboxyphenyl) -5, 5-bis (ethoxycarbonyl) -2-phenylazelaic acid
2- (4- (diethylcarbamoyl) phenyl) -5, 5-bis (ethoxycarbonyl) -2-phenylazelaic acid
5, 5-bis (ethoxycarbonyl) -2- (4-fluorophenyl) -2-phenylazelaic acid
5, 5-bis (ethoxycarbonyl) -2- (2-fluorophenyl) -2-phenylazelaic acid
4, 4-diethyl-1, 7-dimethyl-1-phenyl-1- (o-tolyl) heptane-1, 4, 7-tetracarboxylate
1, 4-diethyl-1, 7-dimethyl-1, 1-di-p-tolylheptane-1, 4, 7-tetracarboxylic acid ester
5, 5-bis (ethoxycarbonyl) -2- (2-fluorophenyl) -2- (4-fluorophenyl) azelaic acid
5, 5-bis (ethoxycarbonyl) -2, 2-bis (4-fluorophenyl) azelaic acid
5, 5-bis (ethoxycarbonyl) -2- (4-fluorophenyl) -2- (4-methoxyphenyl) azelaic acid
9- (6-carboxy-3, 3-bis (ethoxycarbonyl) hexyl) -9H-ton-9-carboxylic acid
3, 3-diethyl-1, 7-dimethyl-1- ([ [1,1' -biphenyl ] -4-yl) heptane-1, 3, 7-tetracarboxylic acid ester
3, 3-diethyl-1, 6-dimethyl-1- ([ [1,1' -biphenyl ] -4-yl) hexane-1, 3, 6-tetracarboxylic acid ester
1- ([ 1,1' -biphenyl ] -4-yl) tetramethyl-1, 3, 6-tetracarboxylate
1, 3-di-tert-butyl-1, 6-dimethyl-1- ([ [1,1' -biphenyl ] -4-yl) hexane-1, 3, 6-tetracarboxylic acid ester
3, 3-diethyl-1, 6-dimethyl-1- (4- (methoxycarbonyl) phenyl) hexane-1, 3, 6-tetracarboxylate
4, 4-bis (ethoxycarbonyl) -2- (4- (ethoxycarbonyl) phenyl) octanedioic acid
3, 3-diethyl-1, 6-dimethyl-1- (4- (diethylcarbamoyl) phenyl) hexane-1, 3, 6-tetracarboxylic acid ester
2- (4-cyanophenyl) -4, 4-bis (ethoxycarbonyl) octanedioic acid
4, 4-bis (ethoxycarbonyl) -2- (4- (((3S, 8S,9S,10R,13S, 14S) -17-acetyl-10, 13-dimethyl-2, 3,4,7,8,9, 10,11,12,13,14,15,16, 17-decatetrahydro-1H-cyclopenta [ a ] phenanthryl-3-yl) carbonyl) phenyl) octanedioic acid
4, 4-bis (ethoxycarbonyl) -2- (4- (((((2-isopropyl-5-methylcyclohexyl) oxy) carbonyl) phenyl) octanedioic acid
2, 2-Diphenyloctanedioic acid
2- ([ [1,1' -biphenyl ] -4-yl) -2-phenyloctanedioic acid
2- ([ [1,1' -biphenyl ] -4-yl) -2-methyloctanedioic acid
2-benzamido-2-phenyloctanedioic acid
4- (2- (benzamido (carboxy) methyl) phenyl) butanoic acid
4- (4- (benzamido (carboxy) methyl) - [1,1' -biphenyl ] -3-yl) butanoic acid
4- (2- (benzamido (carboxy) methyl) -5-fluorophenyl) butanoic acid
4- (2- (benzamido (carboxy) methyl) -5-methylphenyl) butanoic acid
4- (benzamido (carboxy) methyl) -3- (3-carboxypropyl) benzoic acid
4- (2- (benzamido (carboxy) methyl) -5- (ethoxycarbonyl) phenyl) butanoic acid
4- (2- (benzoylamino (carboxy) methyl) -5- (diethylcarbamoyl) phenyl) butanoic acid
4- (2- (benzamido (carboxy) methyl) -5-methoxyphenyl) butyric acid
4- (2- (benzamido (carboxy) methyl) -4-methoxyphenyl) butyric acid
4- (2- (benzamido (carboxy) methyl) -4-phenoxyphenyl) butanoic acid
4- (3- (benzoylamino (carboxy) methyl) - [1,1' -biphenyl ] -4-yl) butanoic acid
4- (2- (benzamido (carboxy) methyl) -4-chlorophenyl) butanoic acid
4- (2- (benzamido (carboxy) methyl) -6-methylphenyl) butanoic acid
4- (2- (benzoylamino (carboxy) methyl) -4, 5-dimethoxyphenyl) butanoic acid
4- (2- (benzoylamino (carboxy) methyl) -5-fluoro-3-methylphenyl) butanoic acid
1 H NMR(400MHz,CD 3 OD)δ7.87–7.76(m,2H),7.54–7.47(m,1H),7.45–7.38(m,2H),7.27(dd,J＝7.5,1.7Hz,1H),7.18–7.08(m,2H),6.00(s,1H),2.86(t,J＝8.5Hz,2H),2.44(t,J＝7.3Hz,2H),2.37(s,3H),1.97–1.83(m,2H)； 13 C NMR(101MHz,CD 3 OD)δ175.77,173.17,168.61,139.16,136.93,134.88,133.80,131.44,130.30,128.11,127.26,126.06,125.24,53.70,33.61,28.37,25.00,18.79；HRMS(ESI-):calculated for C 20 H 19 FNO 5 - [M-H] - 372.1253, found 372.1257.4- (2- (benzoylamino (carboxy) (phenyl) methyl) phenyl) butanoic acid
4- (2- (benzamido (carboxy) methyl) phenyl) -3-methylbutyric acid
4- (4- (carboxy (pivaloylamino) methyl) - [1,1' -biphenyl ] -3-yl) butanoic acid
4- (2- (1- ([ [ (1, 1' -biphenyl ] -4-yl) -1-carboxyethyl) phenyl) butanoic acid
4- (4- (2-carboxypropan-2-yl) - [1,1' -biphenyl ] -3-yl) butanoic acid
4- (2- (1-carboxy-1-phenylethyl) phenyl) butanoic acid
The foregoing is merely exemplary and illustrative of the present invention and it is within the purview of one skilled in the art to modify or supplement the embodiments described or to substitute similar ones without the exercise of inventive faculty, and still fall within the scope of the claims.
Claims (10)
1. A method for synthesizing dicarboxylic acid compounds based on remote carboxylation of non-activated olefin is characterized by comprising the following steps: the olefinic compound, the photocatalyst and the base are added to a reaction vessel and then reacted in CO 2 Adding a reducing agent and a solvent in the atmosphere, stirring and reacting for 0.1-100 h at room temperature under the condition of visible light irradiation, and separating and purifying reaction products to obtain dicarboxylic acid compounds; wherein the molar ratio of the olefin compound, the photocatalyst, the base and the reducing agent is 1.001-0.5;
the structural general formula of the olefin compound is as follows:
wherein R is 1 Is hydrogen, ester group, carboxyl group, amide group, cyano group, aryl group, heteroaryl group, alkynyl group, alkenyl group or alkyl group; r 2 Is hydrogen, ester group, carboxyl group, amide group, cyano group, aryl group, heteroaryl group, alkynyl group, alkenyl group or alkyl group; r 3 Is hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano or alkyl; r 4 Is hydrogen, aryl, heteroaryl, ester group, carboxyl group, amide group, cyano group, fluorine, chlorine, bromine, iodine, boron group, silicon group, phosphine group, thioether group, alkoxy group, acyloxy group, aryloxy group, amine group, alkynyl group, alkenyl group or alkyl group; r 5 Hydrogen, methoxycarbonyl, ethoxycarbonyl or tert-butoxycarbonyl or alkyl; r is 6 Is hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano or alkyl; r 7 Is hydrogen, aryl, heteroaryl, ester group, carboxyl group, amide group, cyano group, fluorine, chlorine, bromine, iodine, boron group, silicon group, phosphine group, thioether group, alkoxy group, acyloxy group, aryloxy group, amine group, alkynyl group, alkenyl group or alkyl group; r 8 Is hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano or alkyl; r is 9 Is hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano or alkyl; r 10 Is hydrogen, aryl, heteroaryl, ester group, carboxyl group, amide group, cyano group, fluorine, chlorine, bromine, iodine, boron group, silicon group, phosphine group, thioether group, alkoxy group, acyloxy group, aryloxy group, amine group, alkynyl group, alkenyl group or alkyl group; r 11 Is hydrogen or alkyl; n is 1 or 2 or 3; the dotted ring is an aromatic or heteroaromatic ring.
2. The method for remotely carboxylating and synthesizing dicarboxylic acid compounds based on non-activated olefin according to claim 1, wherein the molar ratio of the olefin compound, the photocatalyst, the base and the reducing agent is 1.005-0.1.
3. The method for the remote carboxylation synthesis of dicarboxylic acid compounds based on non-activated olefin according to claim 1 or 2, wherein the structural formula of the olefin compound is as follows:
4. the method for the remote carboxylation synthesis of dicarboxylic acid compounds based on non-activated olefin according to claim 1 or 2, wherein the photocatalyst is a D-A type photocatalyst or an Ir photocatalyst.
5. The method for the remote carboxylation synthesis of dicarboxylic acids based on non-activated olefin according to claim 1 or 2, wherein the base is carbonate, bicarbonate, fluoride, tert-butoxide, phosphate, hydrogen phosphate, carboxylate, or an organic base.
6. The method for the remote carboxylation synthesis of dicarboxylic acids based on non-activated olefin according to claim 5, wherein the carbonate is Cs 2 CO 3 、K 2 CO 3 、Na 2 CO 3 Or Li 2 CO 3 (ii) a The bicarbonate is CsHCO 3 、KHCO 3 Or NaHCO 3 (ii) a The fluoride salt is CsF or KF; the tert-butoxide is KO t Bu、NaO t Bu or LiO t Bu; the phosphate is K 3 PO 4 Or Na 3 PO 4 (ii) a The carboxylate is CsOAc, KOAc, naOAc, csOPiv or KOPiv; the organic base is DBU, TBD, DABCO, TMG or DBN.
7. The method for the remote carboxylation synthesis of dicarboxylic acid compounds based on non-activated olefin according to claim 1 or 2, wherein the reducing agent is an organic amine compound.
8. The method for the remote carboxylation synthesis of dicarboxylic acid compounds based on non-activated olefin according to claim 7, wherein the organic amine compound is Cy 2 NEt、Cy 2 NMe、 i Pr 2 NEt、NEt 3 DABCO or PMP.
9. The method for synthesizing dicarboxylic acids based on the remote carboxylation of non-activated olefin according to claim 1, wherein the wavelength of visible light is 400-560 nm, the power of visible light is 3-60W, and the pressure of carbon dioxide is 0.5-30 times atmospheric pressure.
10. The method for the remote carboxylation synthesis of dicarboxylic acids based on non-activated olefin according to claim 1, wherein the solvent concentration is 0.01-10.0M.
Priority Applications (1)
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018010932A1 (en) * | 2016-07-15 | 2018-01-18 | Fundació Institut Català D'investigació Química | Catalytic carboxylation of activated alkanes and/or olefins |
| JP2018162221A (en) * | 2017-03-24 | 2018-10-18 | 公益財団法人乙卯研究所 | Arylpyrrolidine dicarboxylic acid amide derivative |
| CN108752232A (en) * | 2018-05-14 | 2018-11-06 | 四川大学 | A kind of synthetic method of α-quaternary carbon amino acid |
| CN109320481A (en) * | 2018-09-03 | 2019-02-12 | 南京大学 | A kind of decarboxylation alkylation of carboxylic acid NHPI ester and its application in synthesis of diaryl derivative |
| CN110028403A (en) * | 2019-04-19 | 2019-07-19 | 四川大学 | A kind of method of synthesizing succinic acid class compound |
| CN111777477A (en) * | 2019-10-25 | 2020-10-16 | 四川大学 | Method for synthesizing succinic acid derivative or 3-aryl propionic acid |
| CN112079678A (en) * | 2020-07-30 | 2020-12-15 | 四川大学 | Method for constructing carboxylic acid or alcohol by olefin remote functionalization |
| US11040939B1 (en) * | 2020-06-23 | 2021-06-22 | National Cheng Kung University | N-transfer reagent and method for preparing the same and its application |
| WO2021150844A1 (en) * | 2020-01-24 | 2021-07-29 | Sirrus, Inc. | Compositions containing 1,1-disubstituted activated alkenes useful in additive manufacturing and articles formed therefrom |
-
2021
- 2021-09-22 CN CN202111106015.2A patent/CN115838330B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018010932A1 (en) * | 2016-07-15 | 2018-01-18 | Fundació Institut Català D'investigació Química | Catalytic carboxylation of activated alkanes and/or olefins |
| JP2018162221A (en) * | 2017-03-24 | 2018-10-18 | 公益財団法人乙卯研究所 | Arylpyrrolidine dicarboxylic acid amide derivative |
| CN108752232A (en) * | 2018-05-14 | 2018-11-06 | 四川大学 | A kind of synthetic method of α-quaternary carbon amino acid |
| CN109320481A (en) * | 2018-09-03 | 2019-02-12 | 南京大学 | A kind of decarboxylation alkylation of carboxylic acid NHPI ester and its application in synthesis of diaryl derivative |
| CN110028403A (en) * | 2019-04-19 | 2019-07-19 | 四川大学 | A kind of method of synthesizing succinic acid class compound |
| CN111777477A (en) * | 2019-10-25 | 2020-10-16 | 四川大学 | Method for synthesizing succinic acid derivative or 3-aryl propionic acid |
| WO2021150844A1 (en) * | 2020-01-24 | 2021-07-29 | Sirrus, Inc. | Compositions containing 1,1-disubstituted activated alkenes useful in additive manufacturing and articles formed therefrom |
| US11040939B1 (en) * | 2020-06-23 | 2021-06-22 | National Cheng Kung University | N-transfer reagent and method for preparing the same and its application |
| CN112079678A (en) * | 2020-07-30 | 2020-12-15 | 四川大学 | Method for constructing carboxylic acid or alcohol by olefin remote functionalization |
Non-Patent Citations (11)
| Title |
|---|
| "Carboxyzincation Employing Carbon Dioxide and Zinc Powder: Cobalt-Catalyzed Multicomponent Coupling Reactions with Alkynes", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 138, no. 17, 4 May 2016 (2016-05-04), pages 5547 - 5550 * |
| LEI SONG，DA-GANG YU，等: "Visible-light photocatalytic di- and hydro-carboxylation of unactivated alkenes with CO2", NATURE CATALYSIS, vol. 5, no. 9, 26 September 2022 (2022-09-26), pages 832 - 838 * |
| SONG LEI，等: "Visible-Light Photoredox-Catalyzed Remote Difunctionalizing Carboxylation of Unactivated Alkenes with CO2", ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, vol. 59, no. 47, 28 September 2020 (2020-09-28), pages 21121 - 21128 * |
| 关保川;许孝良;王红;李小年;: "可见光催化脱羧偶联反应研究进展", 有机化学, no. 07, 31 December 2016 (2016-12-31), pages 1564 - 1671 * |
| 刘文竹;豆立娟;母伟花;: "环丙烷与不饱和化合物发生[3+2]扩环反应的研究进展", 有机化学, no. 05, 31 December 2020 (2020-12-31), pages 81 - 107 * |
| 吴中乾，等: "均相光催化CO2参与的羧化反应进展", 科学通报, vol. 66, no. 7, 10 March 2021 (2021-03-10), pages 773 - 797 * |
| 张振，等: "可见光促进二氧化碳参与的羧基化反应", 高等学校化学学报, vol. 43, no. 7, 10 July 2022 (2022-07-10), pages 118 - 145 * |
| 徐佩;汪顺义;方毅;纪顺俊;: "二氧化碳与亲核试剂反应的研究进展", 有机化学, no. 07, 15 July 2018 (2018-07-15), pages 74 - 85 * |
| 肖汉至，等: "可见光催化二氧化碳参与非活化烯烃1, 3-双羧基化反应", CHINESE JOURNAL OF CATALYSIS, vol. 50, no. 7, 25 July 2023 (2023-07-25), pages 222 - 228 * |
| 袁莉;李增增;蒋圣明;朱勇;雷千;夏绿露;李岚;余健;张娟;唐石;: "可见光诱导烯烃去芳香化成环合成含氟氮杂螺环已二烯酮", 应用化学, no. 02, 10 February 2018 (2018-02-10), pages 66 - 73 * |
| 高俊;王杨丽;周烨;许甲喆;何永辉;: "可见光催化条件下乙腈参与的烯烃双官能团化反应", 化学试剂, no. 08, 31 December 2020 (2020-12-31), pages 119 - 122 * |
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