CN107936047B - A kind of method of ruthenium catalysis methyl esters selective dehydrogenation boronation reaction - Google Patents
A kind of method of ruthenium catalysis methyl esters selective dehydrogenation boronation reaction Download PDFInfo
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- CN107936047B CN107936047B CN201711258499.6A CN201711258499A CN107936047B CN 107936047 B CN107936047 B CN 107936047B CN 201711258499 A CN201711258499 A CN 201711258499A CN 107936047 B CN107936047 B CN 107936047B
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 64
- 150000004702 methyl esters Chemical class 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 82
- 239000012327 Ruthenium complex Substances 0.000 claims abstract description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 117
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- 239000000047 product Substances 0.000 claims description 44
- 150000002894 organic compounds Chemical class 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 40
- 230000005311 nuclear magnetism Effects 0.000 claims description 40
- 238000007789 sealing Methods 0.000 claims description 40
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 20
- 239000003480 eluent Substances 0.000 claims description 20
- 150000002148 esters Chemical class 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000003208 petroleum Substances 0.000 claims description 20
- 238000010791 quenching Methods 0.000 claims description 20
- 230000000171 quenching effect Effects 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 19
- 238000013507 mapping Methods 0.000 claims description 2
- 238000009795 derivation Methods 0.000 abstract description 12
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- -1 methyl esters borate Chemical class 0.000 abstract description 5
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 114
- 238000005160 1H NMR spectroscopy Methods 0.000 description 36
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 19
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 18
- 238000004607 11B NMR spectroscopy Methods 0.000 description 16
- 238000004293 19F NMR spectroscopy Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000006197 hydroboration reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CQKBIUZEUFGQMZ-UHFFFAOYSA-N [Ru].[Au] Chemical compound [Ru].[Au] CQKBIUZEUFGQMZ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000004492 methyl ester group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of method of ruthenium catalysis methyl esters selective dehydrogenation boronation reaction, using the metal ruthenium complex containing norbornadiene (NBD) ligand of hexa-coordinate as catalyst, using methyl ester derivation and connection pinacol borate as reaction substrate, under mild reaction conditions, boronation reaction selectively occurs for the C-H bond of oxygen atom ortho methyl group in efficient catalytic methyl ester derivation, obtains corresponding methyl esters borate products.
Description
Technical field
The present invention relates to a kind of new methods of ruthenium catalysis methyl ester derivation selective dehydrogenation boronation reaction.
Background technique
For methyl esters analog derivative as common are machine compound, skeleton is widely present in drug molecule and natural products
In.Therefore, how methyl esters analog derivative is converted to the organic compound being more worth into organic chemistry filed primary study
Project.In recent years, the reaction of transition metal-catalyzed C-H bond function dough was the most class of challenge and research significance in organic chemistry
One of topic.Wherein, the C-H bond boronation reaction of metal catalytic organic molecule is then most important conversion in C-H bond function dough
One of reaction, product organic boric acid ester constructs new molecular system as very important organic intermediate.Therefore, if
The selective boronation reaction that methyl ester derivation can be directly realized by, which is further converted into more complicated organic compound, not only to be had
There is important economic benefit, and there are also good environmental and social benefits.
C (the sp that organic ester participates at present3)-H take off Hydroboration have not been reported.Meanwhile about organic esters
Alkoxy C-H bond selective dehydrogenation boronation reaction be also not yet found so far.Therefore, more cheap ruthenium gold is developed and used
Metal catalyst is used to be catalyzed the de- Hydroboration of the selectivity generation alkoxy C-H bond of methyl ester derivation and organic boric acid ester
With very big research significance.
Summary of the invention
The purpose of the present invention is realize that boron selectively occurs for the C-H bond of oxygen atom ortho methyl group in methyl ester derivation for the first time
Change reaction, provides a kind of new strategies for laboratory preparation and the novel methyl esters borate of industrial production.
According to the present invention, the new method of the method ruthenium catalysis methyl ester derivation selective dehydrogenation boronation reaction, feature
It is that the method includes the metal ruthenium complexs containing norbornadiene (NBD) ligand using hexa-coordinate as catalyst, with methyl esters
Derivative and connection pinacol borate are reaction substrate, with tetrahydrofuran (THF), 120 DEG C of reaction temperatures and inert gas shielding
Under, de- Hydroboration selectively occurs for the C-H bond of oxygen atom ortho methyl group in efficient catalytic methyl ester derivation, obtains corresponding
Methyl esters borate products.Its reaction equation are as follows:
Wherein, the reflecting point of substrate methyl ester derivation is the C-H bond of oxygen atom ortho methyl group.
Wherein, borine is connection pinacol borate.
Wherein, catalyst are as follows: hexa-coordinate contains the ruthenium complex of norbornadiene (NBD) ligand.
Wherein, connection pinacol borate dosage is 1 equivalent of substrate methyl ester derivation.
Wherein, catalyst ruthenium complex dosage is 1-4mol%.
Wherein, this reaction dissolvent is tetrahydrofuran (THF).
Wherein, reaction substrate is methyl ester derivation.
Wherein, it is characterised in that: the reaction time is 12 hours, and reaction temperature is 120 DEG C.
Wherein, it is of the invention after reaction, product and yield can be directly obtained by column chromatography for separation.
It is as follows that ruthenium is catalyzed the anti-process of methyl ester derivation selective dehydrogenation boronation:
In argon gas glove box, ruthenium complex (3.0mg, 5.6 μ are sequentially added into the 5mL tube sealing with stirrer
), mol ester substrate (0.56mmol), B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened
And it removes glove box and is placed in heating stirring under 120 DEG C of oil bath and react 12 hours.When reaction solution is cooled to room temperature, acetic acid is used
Ethyl ester quenching reaction, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, two with substrate equimolar amounts are added
Nuclear-magnetism yield of the bromomethane as interior mapping product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again.
By crossing pillar separating-purifying, eluent used is ethyl acetate and petroleum ether, collects the organic phase of product, drains organic molten
Target product is obtained after agent.
Specific embodiment
Below with reference to specific embodiment, the present invention will be further described, and specific embodiments of the present invention are merely to illustrate
Technical solution of the present invention, and the non-limiting present invention.
Embodiment 1, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Colorless and transparent oily object, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product
's1H NMR yield: 81%, separate yield: 56%, 87mg.1H NMR(300MHz,CDCl3) δ 7.94 (d, J=4.0Hz,
2H), 7.22 (d, J=4.0Hz, 2H), 3.94 (s, 2H), 2.40 (s, 3H), 1.28 (s, 12H)11B NMR(192MHz,
CDCl3) δ30.90.13C NMR(101MHz,CDCl3)δ168.0,143.5,129.7,129.0,127.1,83.9,24.7,
21.6. HRMS(EI+):m/z:[M]+calculated for:C15H21O4B:275.1569；found:275.1564.
Embodiment 2, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Colorless and transparent oily object, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product
's1H NMR yield: 70%, separate yield: 51%, 79mg.1H NMR(400MHz,CDCl3) δ 7.90 (d, J=4.0Hz,
1H), 7.36 (t, J=8.0Hz, 1H), 7.23-7.20 (m, 2H), 3.92 (s, 2H), 2.58 (s, 3H), 1.28 (s, 12H)11B
NMR (192MHz,CDCl3)δ30.83.13C NMR(101MHz,CDCl3)δ169.1,140.1,131.9,131.5,130.6,
129.4, 125.6,83.9,24.7,21.6.HRMS(EI+):m/z:[M]+calculated for:C15H21O4B:
275.1569；found: 275.1572.
Embodiment 3, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Colorless and transparent oily object, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product
's1H NMR yield: 90%, separate yield: 61%, 99mg.1H NMR(400MHz,CDCl3) δ 7.99 (d, J=4.0Hz,
2H), 6.88 (d, J=4.0Hz, 2H), 3.90 (s, 2H), 3.82 (s, 3H), 1.27 (s, 12H)11B NMR(192MHz,
CDCl3) δ30.75.13C NMR(101MHz,CDCl3)δ167.9,163.3,131.8,122.1,113.5,83.8,55.4,
24.7. HRMS(EI+):m/z:[M]+calculated for:C15H21O5B:291.1516；found:291.1514.
Embodiment 4, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Light yellow oil, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product1H
NMR yield: 61%, separate yield: 40%, 65mg.1H NMR(300MHz,CDCl3) δ 7.81 (d, J=4.0Hz, 1H), 7.45
(t, J=8.0Hz, 1H), 6.99-6.94 (m, 2H), 3.95 (s, 2H), 3.88 (s, 3H), 1.28 (s, 12H)11B NMR(192
MHz,CDCl3)δ30.72.13C NMR(101MHz,CDCl3)δ167.7,159.1,133.5,131.8,120.0,112.0,
83.9,55.9,24.7.HRMS(EI+):m/z:[M]+calculated for:C15H21O5B:291.1518；found:
291.1522.
Embodiment 5, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Light yellow oil, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:80-1:40.Product1H
NMR yield: 77%, separate yield: 49%, 0.18g.1H NMR(400MHz,CDCl3) δ 8.15 (d, J=4.0Hz, 2H),
7.68 (d, J=4.0Hz, 2H), 4.01 (s, 2H), 1.27 (s, 12H)19F NMR(376MHz,CDCl3)δ-63.12. 11B
NMR(192MHz,CDCl3)δ31.18.13C NMR(101MHz,CDCl3)δ166.3,134.2,133.3,130.5, 125.3,
123.6,84.2,24.6.HRMS(EI+):m/z:[M]+calculated for:C15H18O4BF3:329.1287；found:
329.1289.
Embodiment 6, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Colorless and transparent oily object, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product
's1H NMR yield: 80%, separate yield: 56%, 82mg.1H NMR(400MHz,CDCl3) δ 8.05 (d, J=4.0Hz,
2H), 7.54 (t, J=8.0Hz, 1H), 7.42 (t, J=8.0Hz, 2H), 3.97 (s, 2H), 1.28 (s, 12H)11B NMR(192
MHz,CDCl3)δ30.94.13C NMR(101MHz,CDCl3)δ167.7,132.8,129.9,129.7,128.2,84.0,
24.7. HRMS(EI+):m/z:[M]+calculated for:C14H19O4B:261.1413；found:261.1416.
Embodiment 7, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.White solid, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:5-1:1.Product1H NMR
Yield: 80%, separate yield: 63%, 2.4g.1H NMR(300MHz,CDCl3) δ 7.92 (d, J=4.5Hz), 6.64 (d, J=
4.5Hz),3.83(s,2H),3.05(s,6H),1.28(s,12H).13C NMR(101MHz,CDCl3)δ170.8,153.7,
131.8,114.7,110.6,82.9,40.0,24.8.11B NMR(192MHz,CDCl3)δ27.17.Elemental
analysis, calcd for C16H24BNO4(305.18):C,62.97；H,7.93；N,4.59.Found:C,62.71；H,
7.77；N,4.77.
Embodiment 8, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Light yellow oil, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:80-1:40.Product1H
NMR yield: 70%, separate yield: 47%, 42mg.1H NMR(400MHz,CDCl3)δ8.07(s,1H), 7.87-7.84(m,
2H),7.46-7.37(m,2H),4.02(s,2H),1.29(s,12H).11B NMR(192MHz,CDCl3)δ 31.39.13C NMR
(101MHz,CDCl3)δ163.7,142.2,138.7,133.3,130.6,126.8,125.5,124.8,122.7, 84.3,
24.7.HRMS(EI+):m/z:[M]+calculated for:C16H19O4BS:317.1133；found:317.1135.
Embodiment 9, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Colorless and transparent oily object, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product
's1H NMR yield: 75%, separate yield: 50%, 0.15g.1H NMR(400MHz,CDCl3)δ8.08-8.04(m,2H),
7.08 (t, J=8.0Hz, 2H), 3.96 (s, 2H), 1.28 (s, 12H)11B NMR(192MHz,CDCl3)δ31.18.19F NMR
(376MHz,CDCl3)δ-106.01.13C NMR(101MHz,CDCl3)δ167.1,166.9,164.6,132.4,126.4,
115.5,84.3,24.8.HRMS(EI+):m/z:[M]+calculated for:C14H18O4BF:279.1319；found:
279.1316.
Embodiment 10, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.28g, 1.12mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Light yellow oil, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product1H
NMR yield: 10%, separate yield: 4%, 4mg.1H NMR(400MHz,CDCl3) δ 8.45 (d, J=2.0Hz, 1H), 8.13
(t, J=8.0Hz, 1H), 7.06 (t, J=8.0Hz, 1H), 3.96 (s, 2H), 1.36 (s, 12H), 1.28 (s, 12H)11B NMR
(192MHz,CDCl3)δ30.06.13C NMR(101MHz,CDCl3)δ171.2,168.6,166.8,139.2,135.2,
125.8,115.5,84.2,84.1,24.8,24.7.19F NMR(376MHz,CDCl3)δ-95.79.HRMS(EI+):m/z:
[M]+calculated for:C20H29O6B2F:404.2207；found:404.2205.
Embodiment 11, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Light yellow oil, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product1H
NMR yield: 62%, separate yield: 37%, 0.11g.1H NMR(400MHz,CDCl3) δ 7.90 (t, J=8.0Hz, 1H),
7.48-7.43 (m, 1H), 7.1 (t, J=8.0Hz, 1H), 7.07 (t, J=8.0Hz, 1H), 3.95 (s, 2H), 1.24 (s,
12H).11B NMR(192MHz,CDCl3)δ31.26.13C NMR(101MHz,CDCl3)δ165.3,163.2,160.6,134.3,
132.2, 123.8,116.8,84.1,24.7.19F NMR(376MHz,CDCl3)δ-109.44.HRMS(EI+):m/z:[M]+
calculated for:C14H18O4BF:279.1319；found:279.1320.
Embodiment 12, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.28g, 1.12mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Light yellow oil, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product1H
NMR yield: 9%, separate yield: 5%, 23mg.19F NMR(376MHz,CDCl3)δ-111.26.1H NMR (400MHz,
CDCl3) δ 7.90 (t, J=8.0Hz, 1H), 7.58-7.50 (m, 1H), 7.17 (t, J=8.0Hz, 1H), 3.99 (s, 2H),
1.33(s,12H),1.27(s,12H).13C NMR(101MHz,CDCl3)δ133.9,131.4,129.4,127.7,122.6,
84.4,84.2,24.9,24.7.HRMS(EI+):m/z:[M]+calculated for:C20H29O6B2F:404.2207；found:
404.2209.
Embodiment 13, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.28g, 1.12mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.White oil object, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product1H
NMR yield: 81%, separate yield: 57%, 0.14g.1H NMR(400MHz,CDCl3)δ8.10(s,4H),4.01(s,4H),
1.28(s,24H).11B NMR(192MHz,CDCl3)δ31.23.13C NMR(101MHz,CDCl3)δ166.8,133.7,
129.6,84.2,24.7.Elemental analysis,calcd for C22H32O8B2(446.11):C,59.23；H,
7.23.Found:C, 59.77；H,7.60.
Embodiment 14, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Colorless and transparent oily object, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product
's1H NMR yield: 58%, separate yield: 27%, 50mg.1H NMR(400MHz,CDCl3) δ 8.01 (d, J=4.0Hz,
1H), 7.86 (d, J=4.0Hz, 1H), 7.80-7.78 (m, 1H), 7.55-7.47 (m, 2H), 7.44 (s, 1H), 7.43 (d, J=
1.0 Hz,1H),4.12(s,2H),3.81(s,2H),1.23(s,12H).11B NMR(192MHz,CDCl3)δ31.17.13C
NMR (101MHz,CDCl3)δ172.6,133.8,132.1,130.7,128.6,128.0,127.9,126.2,125.7,
125.4,124.1, 84.11,38.7,24.7.HRMS(EI+):m/z:[M]+calculated for:C19H23O4B:
325.1726；found:325.1723.
Embodiment 15, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Light yellow oil, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product1H
NMR yield: 70%, separate yield: 51%, 39mg.1H NMR(300MHz,CDCl3)δ7.29-7.24(m,5H),3.78 (s,
2H),3.66(s,2H),1.24(s,12H).13C NMR(101MHz,CDCl3)δ172.7,134.1,129.3,128.4,
126.9,84.1,40.8,24.7.HRMS(EI+):m/z:[M]+calculated for:C15H21O4B:275.1569；found:
275.1564.
Embodiment 16, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Light yellow oil, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product1H
NMR yield: 56%, separate yield: 26%, 15mg.1H NMR(300MHz,CDCl3)δ3.72(s,2H),2.06(s, 3H),
1.25(s,12H).11B NMR(192MHz,CDCl3)δ30.98.13C NMR(101MHz,CDCl3)δ172.2, 84.0,24.7,
20.5.HRMS(EI+):m/z:[M]+calculated for:C18H14O4B:184.1021；found:184.1017.
Embodiment 17, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Colorless and transparent oily object, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product
's1H NMR yield: 57%, separate yield: 32%, 22mg.1H NMR(400MHz,CDCl3)δ3.77(s,2H),3.65(t, J
=4.0Hz, 2H), 3.33 (s, 3H), 2.60 (t, J=8.0Hz, 2H), 1.25 (s, 12H)11B NMR(192MHz,CDCl3)δ
31.03.13C NMR(101MHz,CDCl3)δ172.6,84.1,68.0,58.7,34.6,24.7.HRMS(EI+):m/z:[M]+
calculated for:C10H18O5B:228.1284；found:228.1281.
Embodiment 18, wherein methyl esters substrate is as follows:
Methyl esters substrate structure formula:
Ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate (0.56 are being sequentially added into the 5mL tube sealing with stirrer
mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofuran.Then the 5mL tube sealing is tightened and removes glove box juxtaposition
Heating stirring is reacted 12 hours under 120 DEG C of oil bath.When reaction solution is cooled to room temperature, with ethyl acetate quenching reaction, with
Afterwards by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide with substrate equimolar amounts is added as internal standard
The nuclear-magnetism yield for surveying product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through pillar
Separating-purifying.Colorless and transparent oily object, crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.Product
's1H NMR yield: 64%, separate yield: 34%, 26mg.1H NMR(400MHz,CDCl3)δ3.70(s,2H), 2.38-
2.31(m,1H),1.90-1.86(m,2H),1.75-1.62(m,4H),1.48-1.39(m,2H),1.26-1.28(m,2H),
1.25(s,12H).11B NMR(192MHz,CDCl3)δ30.73.13C NMR(101MHz,CDCl3)δ177.5,83.8, 42.6,
29.0,25.7,25.3,24.7.HRMS(EI+):m/z:[M]+calculated for:C14H25O4B:267.1882；found:
267.1877.
It should be noted that foregoing invention content and specific embodiment are intended to prove technical solution provided by the present invention
Practical application should not be construed as limiting the scope of the present invention.Those skilled in the art are in spirit and principles of the present invention
It is interior, when can various modifications may be made, equivalent replacement or improve.Protection scope of the present invention is subject to the appended claims.
Claims (1)
1. a kind of method of ruthenium catalysis methyl esters selective dehydrogenation boronation reaction, which is characterized in that the methyl esters substrate are as follows:The product are as follows:The ruthenium complex are as follows:Institute
The reaction process stated are as follows: sequentially add ruthenium complex 3.0mg, 5.6 μm of ol, ester substrate into the 5mL tube sealing with stirrer
0.56mmol,B2pin2The 5mL tube sealing is then tightened and removes glove box simultaneously by 0.14g, 0.56mmol and 1mL tetrahydrofuran
Heating stirring is placed under 120 DEG C of oil bath to react 12 hours, when reaction solution is cooled to room temperature, with ethyl acetate quenching reaction,
Then by low-boiling-point organic compound in being drained on Rotary Evaporators, finally, in the conduct of the methylene bromide of addition and substrate equimolar amounts
The nuclear-magnetism yield of mapping product obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passing through column
Sub- separating-purifying obtains colorless and transparent oily object, and crossing the eluent that pillar uses is ethyl acetate: petroleum ether=1:40-1:10.
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