CN107936047A - A kind of new method of ruthenium catalysis methyl esters selective dehydrogenation boronation reaction - Google Patents
A kind of new method of ruthenium catalysis methyl esters selective dehydrogenation boronation reaction Download PDFInfo
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- CN107936047A CN107936047A CN201711258499.6A CN201711258499A CN107936047A CN 107936047 A CN107936047 A CN 107936047A CN 201711258499 A CN201711258499 A CN 201711258499A CN 107936047 A CN107936047 A CN 107936047A
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- 150000004702 methyl esters Chemical class 0.000 title claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 83
- 239000012327 Ruthenium complex Substances 0.000 claims abstract description 26
- 238000009795 derivation Methods 0.000 claims abstract description 19
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 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 claims abstract description 7
- -1 methyl esters borate Chemical class 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 7
- 238000006197 hydroboration reaction Methods 0.000 claims abstract description 5
- 239000003446 ligand Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 35
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 229910000085 borane Inorganic materials 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000004492 methyl ester group Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 20
- 230000004044 response Effects 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 114
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 111
- 150000002894 organic compounds Chemical class 0.000 description 40
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 38
- 230000005311 nuclear magnetism Effects 0.000 description 38
- 238000007789 sealing Methods 0.000 description 38
- 238000005160 1H NMR spectroscopy Methods 0.000 description 36
- 239000000047 product Substances 0.000 description 34
- 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
- 239000012043 crude product Substances 0.000 description 19
- 239000003480 eluent Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 19
- 239000007788 liquid Substances 0.000 description 19
- 238000013507 mapping Methods 0.000 description 19
- 239000003208 petroleum Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 18
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 18
- 238000004607 11B NMR spectroscopy Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 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
- 0 *COC(c1ccccc1)=O Chemical compound *COC(c1ccccc1)=O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 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
- 229910052796 boron Inorganic materials 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 238000005516 engineering process Methods 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
- 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
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 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
The present invention relates to a kind of new method of ruthenium catalysis methyl ester derivation 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.At present, the selective dehydrogenation boronation reaction on oxygen atom ortho methyl group C-H bond in ester derivative is not yet reported.The present invention realizes that the de- Hydroboration of oxygen atom ortho methyl group selectively occurs for methyl ester derivation first, and the preparation for this kind of new organic synthesis intermediate of organic ester borate provides a kind of brand-new response strategy.
Description
Technical field
The present invention relates to a kind of new method of ruthenium catalysis methyl ester derivation selective dehydrogenation boronation reaction.
Background technology
For methyl esters analog derivative as common are machine compound, its skeleton is widely present in drug molecule and natural products
In.Therefore, how methyl esters analog derivative is changed into the organic compound that is more worth into organic chemistry filed primary study
Problem.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, its product organic boric acid ester builds new molecular system as very important organic intermediate.Therefore, if
The selective boronation reaction that methyl ester derivation can be directly realized by is further converted into more complicated organic compound and is not only had
There are important economic benefit, and also good environmental and social benefits.
C (the sp that organic ester participates at present3)-H takes off Hydroboration and not yet report.Meanwhile on organic esters
Alkoxy C-H bond selective dehydrogenation boronation reaction be also not yet found so far.Therefore, more cheap ruthenium gold is developed
Metal catalyst is used for the de- Hydroboration for being catalyzed the selectivity generation alkoxy C-H bond of methyl ester derivation and organic boric acid ester
With very big research significance.
The content of the invention
Boron selectively occurs for the C-H bond the purpose of the present invention is realizing oxygen atom ortho methyl group in methyl ester derivation first
Change reaction, prepared for laboratory and the new methyl esters borate of industrial production provides a kind of new strategies.
According to the present invention, the new method of the method ruthenium catalysis methyl ester derivation selective dehydrogenation boronation reaction, its feature
It is the described method includes using the metal ruthenium complex containing norbornadiene (NBD) ligand of 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 is：
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 is：Hexa-coordinate contains the ruthenium complex of norbornadiene (NBD) ligand.
Wherein, 1 equivalent that pinacol borate dosage is substrate methyl ester derivation is joined.
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：When reaction time is 12 small, reaction temperature is 120 DEG C.
Wherein, it is of the invention after reaction, product and yield directly can be obtained by column chromatography for separation.
The anti-process of ruthenium catalysis methyl ester derivation selective dehydrogenation boronation is as follows：
In argon gas glove box, ruthenium complex (3.0mg, 5.6 μ are sequentially added into the 5mL tube sealings with stirrer
), mol ester substrate (0.56mmol), B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened
And remove glove box be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, acetic acid is used
Reaction is quenched in ethyl ester, 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.
Embodiment
Below with reference to specific embodiment, the present invention will be further described, and specific embodiment of the invention is merely to illustrate
Technical scheme, and the non-limiting present invention.
Embodiment 1, wherein methyl esters substrate are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Water white transparency oily thing, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Production
Thing1H NMR yields: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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Water white transparency oily thing, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Production
Thing1H NMR yields: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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Water white transparency oily thing, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Production
Thing1H NMR yields: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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Light yellow oil, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Product
's1HNMR yields: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
(192MHz,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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Light yellow oil, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:80-1:40.Product
's1H NMR yields: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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Water white transparency oily thing, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Production
Thing1H NMR yields: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
(192MHz,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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.White solid, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:5-1:1.Product1H
NMR yields: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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Light yellow oil, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:80-1:40.Product
's1H NMR yields: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)δ31.39.13C
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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Water white transparency oily thing, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Production
Thing1H NMR yields: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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.28g, 1.12mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Light yellow oil, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Product
's1H NMR yields: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)
.11BNMR(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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Light yellow oil, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Product
's1HNMR yields: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).11BNMR(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]+
calculatedfor:C14H18O4BF:279.1319；found:279.1320.
Embodiment 12, wherein methyl esters substrate are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.28g, 1.12mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Light yellow oil, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Product
's1H NMR yields: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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.28g, 1.12mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.White oil thing, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Product
's1H NMR yields: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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Water white transparency oily thing, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Production
Thing1H NMR yields: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=
1.0Hz,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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Light yellow oil, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Product
's1HNMR yields: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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Light yellow oil, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Product
's1HNMR yields: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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Water white transparency oily thing, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Production
Thing1H NMR yields: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 are as follows：
Methyl esters substrate structure formula：
Toward with stirrer 5mL tube sealings in sequentially add ruthenium complex (3.0mg, 5.6 μm of ol), ester substrate
(0.56mmol),B2pin2(0.14g, 0.56mmol) and 1mL tetrahydrofurans.Then the 5mL tube sealings are tightened and removes glove box
Be placed under 120 DEG C of oil bath heating stirring reaction 12 it is small when.When question response liquid is cooled to room temperature, it is quenched instead with ethyl acetate
Should, then by low-boiling-point organic compound in being drained on Rotary Evaporators.Finally, the methylene bromide conduct with substrate equimolar amounts is added
The nuclear-magnetism yield of interior mapping product, obtains extracting the low-boiling-point organic compound in crude product after nuclear-magnetism yield again, finally, passed through
Pillar separating-purifying.Water white transparency oily thing, it is ethyl acetate to cross the eluent that pillar uses：Petroleum ether=1:40-1:10.Production
Thing1H NMR yields: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 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 substitution or improve.Protection scope of the present invention is subject to the appended claims.
Claims (10)
1. a kind of new method of ruthenium catalysis methyl esters selective dehydrogenation boronation reaction, it is characterised in that the described method includes with hexa-coordinate
The metal ruthenium complex containing norbornadiene (NBD) ligand be catalyst, using methyl ester derivation and connection pinacol borate as
Reaction substrate, with tetrahydrofuran (THF), 120 DEG C of reaction temperatures and inert gas shielding, oxygen in efficient catalytic methyl ester derivation
De- Hydroboration selectively occurs for the C-H bond of atom vicinal methyl, obtains corresponding methyl esters borate products.
2. method according to claim 1, the reflecting point of substrate methyl ester derivation is the C-H bond of oxygen atom ortho methyl group.
3. method according to claim 1, borine is connection pinacol borate.
4. method according to claim 1, catalyst are：The ruthenium complex containing norbornadiene (NBD) ligand of hexa-coordinate.
5. according to 1 or 3 the method for claim, connection pinacol borate dosage is 1 equivalent of substrate methyl ester derivation.
6. according to 1 or 4 the method for claim, catalyst ruthenium complex dosage is 1-4mol%.
7. method according to claim 1, this reaction dissolvent is tetrahydrofuran (THF).
8. method according to claims 1 to 7, reaction substrate is methyl ester derivation.
9. the method as described in claim 1, it is characterised in that：When reaction time is 12 small, reaction temperature is 120 DEG C.
10. the method as described in claim 1, it is characterised in that：When after reaction, can directly by column chromatography for separation come
To product and yield.
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| CN111004263A (en) * | 2019-12-26 | 2020-04-14 | 台州学院 | Method for selectively carrying out diboronation reaction on 2-aryl pyridine derivative |
| CN111039967A (en) * | 2019-12-24 | 2020-04-21 | 台州学院 | Method for selectively carrying out boronization reaction on five-membered heterocyclic ring by high-efficiency catalysis |
| CN111039968A (en) * | 2019-12-25 | 2020-04-21 | 台州学院 | Method for catalyzing 2, 3-dihydrobenzofuran derivative to selectively carry out boronization reaction |
| CN111057081A (en) * | 2019-12-25 | 2020-04-24 | 台州学院 | Method for catalyzing selective boronization reaction of 2-alkoxy pyridine |
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| CN111039967A (en) * | 2019-12-24 | 2020-04-21 | 台州学院 | Method for selectively carrying out boronization reaction on five-membered heterocyclic ring by high-efficiency catalysis |
| CN111039968A (en) * | 2019-12-25 | 2020-04-21 | 台州学院 | Method for catalyzing 2, 3-dihydrobenzofuran derivative to selectively carry out boronization reaction |
| CN111057081A (en) * | 2019-12-25 | 2020-04-24 | 台州学院 | Method for catalyzing selective boronization reaction of 2-alkoxy pyridine |
| CN111039968B (en) * | 2019-12-25 | 2022-09-02 | 台州学院 | Method for catalyzing 2, 3-dihydrobenzofuran derivative to selectively carry out boronization reaction |
| CN111004263A (en) * | 2019-12-26 | 2020-04-14 | 台州学院 | Method for selectively carrying out diboronation reaction on 2-aryl pyridine derivative |
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