CN109232529B - Preparation method of Rh (III) catalytic compound with nitrogen heterocyclic skeleton - Google Patents
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 13
- 150000001875 compounds Chemical class 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010948 rhodium Substances 0.000 claims abstract description 19
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001336 alkenes Chemical class 0.000 claims abstract description 9
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000005256 alkoxyacyl group Chemical group 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical group [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 1
- XTBAPWCYTNCZTO-UHFFFAOYSA-N 1H-isoindolone Natural products C1=CC=C2C(=O)N=CC2=C1 XTBAPWCYTNCZTO-UHFFFAOYSA-N 0.000 abstract description 7
- 238000001338 self-assembly Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- -1 aromatic carboxamides Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000003953 γ-lactams Chemical class 0.000 description 2
- 238000007341 Heck reaction Methods 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical compound [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method for constructing an azacyclo skeleton by catalyzing self-assembly guide group-assisted Rh (III), which comprises the following steps: in the presence of rhodium catalyst and acetate, aromatic aldehyde and 2-aminopyridine react in solvent to generate an effective guide group in situ. The guide group reacts with substituted olefin under the catalysis of rhodium, and after the reaction is finished, the nitrogen heterocyclic skeleton compound is obtained through post-treatment. The preparation method uses rhodium for catalysis, and successfully realizes a synthetic strategy of a self-assembly high-efficiency guide base. The reaction starts from simpler raw materials, synthesizes a novel isoindolone framework and an isoquinoline structure with substitution characteristics by utilizing a one-pot method in a simple and mild catalytic system, and has the advantages of simple and convenient operation, mild reaction conditions, high yield and high atom economy.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method for constructing an azacyclic skeleton by catalyzing Rh (III) with self-assembled guide groups.
Background
Isoindolones (γ -lactams) are a more common and important parent nucleus. Since the α -position is an N atom having a strong complexing force, many studies have been reported on the participation of a nitrogen atom in benzamide as a targeting atom in the formation of γ -lactam.
The li-xing-wei-subject group first tried in 2010 to build isoindolone backbones by reaction with acrylates using N-phenyl substituted aromatic carboxamides as substrates (org. lett.,2010,12, 5430). In the reaction, a Heck product intermediate is first produced, and then, Michael addition is carried out to cyclize the product. However, if the aromatic ring in the substrate is a heterocycle such as furan, indole, etc., the isoindolone product is not easily formed, and mostly stays on the oxidation Heck reaction product, and the reaction conditions are harsh. The reaction formula is as follows:
in 2014, the above reaction was improved by the jinquan project group. They use N-perfluoro substituted phenyl aromatic carboxamides as substrates (chem. sci.,2015,6,1923) and actually increase the electron withdrawing ability of the substituents on the nitrogen atoms in the amides, reducing isomerization of the amide bonds and increasing nucleophilicity. Although the work widens the category of the substrate, the method has good applicability to heterocycles such as thiophene, furan and pyridine, and the reaction condition becomes mild, the universality of the substrate is not wide enough, the raw materials are complex, and the preparation process is not simple enough.
Disclosure of Invention
The invention provides a method for constructing an azacyclic skeleton by catalyzing Rh (III) through self-assembly guide groups, which can generate an effective novel guide group in situ, and has the advantages of simple raw materials, mild reaction conditions, high reaction yield and high atom economy.
A preparation method for constructing an azacyclic skeleton by catalyzing self-assembly guide group assisted Rh (III) comprises the following steps: in the presence of rhodium catalyst and acetate, aromatic aldehyde and 2-aminopyridine react in solvent to generate an effective guide group in situ. The guide group reacts with substituted olefin under the catalysis of rhodium, and after the reaction is finished, the nitrogen heterocyclic skeleton compound is obtained through post-treatment.
The structure of the aromatic aldehyde is shown as the formula (I):
the structure of the 2-aminopyridine is shown as a formula (II):
the structure of the substituted olefin is shown as the formula (III):
the structure of the compound with the nitrogen heterocyclic skeleton is shown as a formula (IV):
in the formulas (I) to (IV), R is alkyl, alkoxy, hydrogen atom, halogen atom, cyano, ester group, nitro or trifluoromethyl;
r' is alkoxy acyl, alkanoyl, cyano or amide.
The reaction formula is as follows:
the reaction mechanism is presumed to be:
firstly, aromatic aldehyde and 2-aminopyridine are subjected to condensation reaction to generate an effective novel guide group in situ. As follows:
then, the self-assembly guiding group and the substituted olefin are reacted under the catalysis of metal rhodium (III) as follows:
preferably, the rhodium catalyst is [ Cp RhCl ]2]2(CAS: 12354-85-7) in an amount of 2 mol%, which is highly effective in catalyzing the substrate in the present invention.
Preferably, the acetate is copper acetate, and the dosage is 2 eq. The acetate salt acts as an oxidant to assist in the catalysis of the rhodium catalyst in the reaction.
Preferably, the aromatic aldehyde, the 2-aminopyridine and the substituted olefin are used in a molar ratio of 1:1.2 to 2.
Preferably, R is C1～C5Alkyl radical, C1～C5Alkoxy group, hydrogen atom, halogen atom, cyano group, ester group, nitro group, trifluoromethyl group, and these substituents can facilitate the reaction.
Preferably, R' is C1～C5Alcoxyl acyl radical, C1～C5And the substituents are electron-withdrawing substituents, so that the reactivity of the substituted olefin is improved, and the Michael addition reaction is facilitated.
Preferably, the solvent is at least one of acetonitrile, water, methanol, ethanol, DMF, DMSO, and THF, which are polar solvents that facilitate cleavage of C-H bonds in the substrate, and more preferably, acetonitrile.
Preferably, the reaction temperature is 80 to 110 ℃, and an excessively high reaction temperature increases side reactions, and an excessively low reaction temperature decreases the conversion rate of the reaction product, and more preferably, the reaction temperature is 80 ℃.
Preferably, the reaction atmosphere is one of air and nitrogen, and in these atmospheres, the reaction proceeds better with higher yield, and more preferably, the reaction atmosphere is N2And (4) atmosphere.
In the invention, the reaction time can be monitored by TLC, and the reaction can be completely carried out by stirring for 4-12 hours at 80 ℃.
In order to increase the yield of the reaction, the aromatic aldehyde compound, 2-aminopyridine, Cu (OAc)2And [ Cp RhCl2]2The mixture was charged into a Schlenk flask, and then subjected to vacuum evacuation and then to nitrogen gas introduction, and after three operations, the solvent and the substituted olefin were added.
Compared with the prior art, the invention has the beneficial effects that: the reaction is prepared by a one-pot method, and the operation is simple. The high-efficiency guide group can be generated in the reaction. The synthesized isoindolone skeleton and isoquinoline structure product with novel substitution characteristics has high yield, the raw materials required by the reaction are simple and easy to obtain, the reaction atom economy is high, the catalytic system is simple and mild, and the requirements of green chemistry are met.
Drawings
FIG. 1 is a diagram of the product obtained in example 11HNMR spectrogram;
FIG. 2 shows the product obtained in example 113CNMR spectrogram;
FIG. 3 shows the product obtained in example 21HNMR spectrogram;
FIG. 4 shows the product obtained in example 213CNMR spectrogram.
Detailed Description
Example 1
In a 25mL Schlenk flask, 24mg (0.2mmol) of p-tolualdehyde (1.5eq), Cu (OAc)253mg (2.0eq), 2-aminopyridine 25mg (2.0eq), [ Cp. RhCl2] 23 mg (2%) were weighed in. Then, the mixture was subjected to vacuum pumping and then nitrogen gas was introduced, and after three operations, 2mL of acetonitrile was added and stirred for 10min, and then 45. mu.L (2.0eq) of ethyl acrylate was added and stirred at a constant temperature of 80 ℃ in a nitrogen gas atmosphere. After about 5h, TLC detection reaction is finished, a little silica gel is added, the solvent is evaporated, solidification and solid sample loading are carried out, and column chromatography separation is carried out. The product is obtained in 55mg with a yield of 90%. The reaction formula is as follows:
the physical properties and spectrum data of the product are as follows: a white solid; melting point: 90-92 ℃;1H NMR(CDCl3,600MHz)8.54(d,J＝12.6Hz,1H),8.42-8.40(m,1H),7.81-7.73(m,2H),7.39(s,1H),7.31(d,J＝12Hz,1H),7.07-7.04(m,1H),5.95-5.92(m,1H),4.12-4.08(m,2H),3.33(dd,J1＝24Hz,J2＝5.4Hz),2.81-2.75(m,1H),2.47(s,3H),1.16(t,J＝10.8Hz,3H)ppm；13C NMR(CDCl3,150MHz)170.7,167.7,151.1,147.7,145.4,143.8,138.0,129.8,129.4,124.1,123.3,119.4,115.7,60.7,56.4,38.2,22.2,14.2ppm.
example 2
In a 25mL Schlenk flask, 21mg (0.2mmol) benzaldehyde (1.0eq), Cu (OAc)280mg (2.0eq), 38mg (2.0eq) of 2-aminopyridine, [ Cp + RhCl2]24.96mg (2%). Then, the mixture was subjected to vacuum pumping and then nitrogen gas was introduced thereinto, and after three operations, 2mL of acetonitrile was added thereto and stirred for 10min, 43mL (2.0eq) of ethyl acrylate was further added thereto and stirred at a constant temperature of 80 ℃ in a nitrogen gas atmosphere. TLC detection after about 5hAdding some silica gel, evaporating solvent, solidifying, loading solid, and separating by column chromatography. 51mg of product is obtained, and the yield is 85 percent. The reaction formula is as follows:
the physical properties and spectrum data of the product are as follows: a white solid; melting point: 123-125 ℃;1H NMR(CDCl3,600MHz)8.54(d,J＝11.4Hz,1H),8.42(m,1H),7.92(d,J＝11.4Hz,1H),7.79-7.74(m,1H),7.60(m,2H),7.53-7.49(m,1H),7.09-7.06(m,1H),5.98(m,1H),4.11-4.05(m,2H),3.35(dd,J1＝24Hz,J2＝5.4Hz,1H),2.78(m,1H),1.15(t,J＝10.8Hz,3H)ppm；13C NMR(CDCl3,150MHz)170.7,167.7,151.0,147.9,145.0,138.1,133.0,132.0,128.8,124.4,123.0,119.7,115.9,60.8,56.6,38.2,14.2ppm.。
Claims (6)
1. a preparation method of Rh (III) catalysis compound with nitrogen heterocyclic skeleton is characterized by comprising the following steps: in the presence of a rhodium catalyst and acetate, aromatic aldehyde and 2-aminopyridine react in a solvent to generate an intermediate containing a guide group in situ; the intermediate reacts with substituted olefin under the catalysis of rhodium, and after the reaction is finished, the compound with the nitrogen heterocyclic skeleton is obtained through post-treatment;
the structure of the aromatic aldehyde is shown as the formula (I):
the structure of the 2-aminopyridine is shown as a formula (II):
the structure of the substituted olefin is shown as the formula (III):
the structure of the compound with the nitrogen heterocyclic skeleton is shown as a formula (IV):
in the formulas (I) to (IV), R is C1-C5 alkyl, C1-C5 alkoxy, hydrogen atom, halogen atom, cyano, nitro and trifluoromethyl;
r' is C1-C5 alkoxy acyl, C1-C5 alkanoyl or cyano;
the rhodium catalyst is [ Cp & RhCl2]2；
The acetate is copper acetate.
2. The method of claim 1, wherein the amount of the rhodium catalyst is 2 mol% of the aromatic aldehyde.
3. The method for preparing Rh (III) catalyzed compound with nitrogen heterocyclic skeleton as claimed in claim 1 or 2, wherein the amount of acetate is 1.2-2.0 times of the molar amount of aromatic aldehyde.
4. The method of claim 1, wherein the solvent is at least one of acetonitrile, water, methanol, ethanol, DMF, DMSO, and THF.
5. The method for preparing Rh (III) catalytic compound with nitrogen heterocyclic skeleton as claimed in claim 1, wherein the reaction temperature is 60-110 ℃.
6. The method of claim 1, wherein the atmosphere of the reaction is one of air and nitrogen.
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