CN115710287A - Ring-opening boronization reaction method of cyclopropane compound under condition of no metal catalysis - Google Patents
Ring-opening boronization reaction method of cyclopropane compound under condition of no metal catalysis Download PDFInfo
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- CN115710287A CN115710287A CN202211518968.4A CN202211518968A CN115710287A CN 115710287 A CN115710287 A CN 115710287A CN 202211518968 A CN202211518968 A CN 202211518968A CN 115710287 A CN115710287 A CN 115710287A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 84
- -1 cyclopropane compound Chemical class 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 18
- 238000007142 ring opening reaction Methods 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 192
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims abstract description 134
- 150000001875 compounds Chemical class 0.000 claims abstract description 63
- 239000012298 atmosphere Substances 0.000 claims abstract description 43
- PKLFICDRWXSEJK-UHFFFAOYSA-N B.C1(=CC=CC2=CC=CC=C12)O Chemical compound B.C1(=CC=CC2=CC=CC=C12)O PKLFICDRWXSEJK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 150
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 21
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 19
- 150000001942 cyclopropanes Chemical class 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Chemical group 0.000 claims description 3
- 239000011593 sulfur Chemical group 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 6
- 125000001559 cyclopropyl group Chemical class [H]C1([H])C([H])([H])C1([H])* 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 119
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 111
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 111
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 80
- 238000002360 preparation method Methods 0.000 description 56
- 229910052757 nitrogen Inorganic materials 0.000 description 39
- 238000012512 characterization method Methods 0.000 description 37
- 238000010828 elution Methods 0.000 description 37
- 238000010898 silica gel chromatography Methods 0.000 description 37
- IASIJDXUZOLTAH-UHFFFAOYSA-N n-cyclopropylbenzamide Chemical compound C=1C=CC=CC=1C(=O)NC1CC1 IASIJDXUZOLTAH-UHFFFAOYSA-N 0.000 description 20
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KOXKBSLHRBNBNI-UHFFFAOYSA-N n-(1-methylcyclopropyl)benzamide Chemical compound C=1C=CC=CC=1C(=O)NC1(C)CC1 KOXKBSLHRBNBNI-UHFFFAOYSA-N 0.000 description 3
- VPHKQMTVHJDHSU-UHFFFAOYSA-N n-(1-phenylcyclopropyl)benzamide Chemical compound C=1C=CC=CC=1C(=O)NC1(C=2C=CC=CC=2)CC1 VPHKQMTVHJDHSU-UHFFFAOYSA-N 0.000 description 3
- DREYJVRZLKQJDG-UHFFFAOYSA-N n-cyclopropylthiophene-2-carboxamide Chemical compound C=1C=CSC=1C(=O)NC1CC1 DREYJVRZLKQJDG-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- VMRXNYYUXQFGFK-UHFFFAOYSA-N 2-chloro-n-cyclopropylbenzamide Chemical compound ClC1=CC=CC=C1C(=O)NC1CC1 VMRXNYYUXQFGFK-UHFFFAOYSA-N 0.000 description 2
- NVRCUSXYDRRGSV-UHFFFAOYSA-N 3-chloro-n-cyclopropylbenzamide Chemical compound ClC1=CC=CC(C(=O)NC2CC2)=C1 NVRCUSXYDRRGSV-UHFFFAOYSA-N 0.000 description 2
- JHJAFIHZCMPVQS-UHFFFAOYSA-N 4-acetyl-n-cyclopropylbenzamide Chemical compound C1=CC(C(=O)C)=CC=C1C(=O)NC1CC1 JHJAFIHZCMPVQS-UHFFFAOYSA-N 0.000 description 2
- PTAOXRHPDPMIBL-UHFFFAOYSA-N 4-bromo-n-cyclopropylbenzamide Chemical compound C1=CC(Br)=CC=C1C(=O)NC1CC1 PTAOXRHPDPMIBL-UHFFFAOYSA-N 0.000 description 2
- IKEOHQKJEPBWLC-UHFFFAOYSA-N 4-chloro-n-cyclopropylbenzamide Chemical compound C1=CC(Cl)=CC=C1C(=O)NC1CC1 IKEOHQKJEPBWLC-UHFFFAOYSA-N 0.000 description 2
- XTUAPAIXLWGBPU-UHFFFAOYSA-N 4-tert-butyl-n-cyclopropylbenzamide Chemical compound C1=CC(C(C)(C)C)=CC=C1C(=O)NC1CC1 XTUAPAIXLWGBPU-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000005271 boronizing Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- OWXPHZLYDIDNFZ-UHFFFAOYSA-N n-cyclopropyl-2,2-dimethylpropanamide Chemical compound CC(C)(C)C(=O)NC1CC1 OWXPHZLYDIDNFZ-UHFFFAOYSA-N 0.000 description 2
- MBEQTAXXGZVTGQ-UHFFFAOYSA-N n-cyclopropyl-2,3,4,5,6-pentafluorobenzamide Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1C(=O)NC1CC1 MBEQTAXXGZVTGQ-UHFFFAOYSA-N 0.000 description 2
- UTJOZVQZEZJWFR-UHFFFAOYSA-N n-cyclopropyl-2-methylbenzamide Chemical compound CC1=CC=CC=C1C(=O)NC1CC1 UTJOZVQZEZJWFR-UHFFFAOYSA-N 0.000 description 2
- IKWAFPZZUUASMP-UHFFFAOYSA-N n-cyclopropyl-3-methylbenzamide Chemical compound CC1=CC=CC(C(=O)NC2CC2)=C1 IKWAFPZZUUASMP-UHFFFAOYSA-N 0.000 description 2
- BLJZGFYVMHVFHW-UHFFFAOYSA-N n-cyclopropyl-4-(trifluoromethyl)benzamide Chemical compound C1=CC(C(F)(F)F)=CC=C1C(=O)NC1CC1 BLJZGFYVMHVFHW-UHFFFAOYSA-N 0.000 description 2
- YPSPTZQFKWMPDX-UHFFFAOYSA-N n-cyclopropyl-4-fluorobenzamide Chemical compound C1=CC(F)=CC=C1C(=O)NC1CC1 YPSPTZQFKWMPDX-UHFFFAOYSA-N 0.000 description 2
- VEHNJDQSMLMENP-UHFFFAOYSA-N n-cyclopropyl-4-methoxybenzamide Chemical compound C1=CC(OC)=CC=C1C(=O)NC1CC1 VEHNJDQSMLMENP-UHFFFAOYSA-N 0.000 description 2
- BRCUSPLHYFOGLC-UHFFFAOYSA-N n-cyclopropyl-4-methylbenzamide Chemical compound C1=CC(C)=CC=C1C(=O)NC1CC1 BRCUSPLHYFOGLC-UHFFFAOYSA-N 0.000 description 2
- HPXHDFCHLKARTL-UHFFFAOYSA-N n-cyclopropyl-4-nitrobenzamide Chemical compound C1=CC([N+](=O)[O-])=CC=C1C(=O)NC1CC1 HPXHDFCHLKARTL-UHFFFAOYSA-N 0.000 description 2
- NTRUUEGSGXDSEC-UHFFFAOYSA-N n-cyclopropyl-4-phenylbenzamide Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)NC1CC1 NTRUUEGSGXDSEC-UHFFFAOYSA-N 0.000 description 2
- UBCVRGSRJOQNPT-UHFFFAOYSA-N n-cyclopropyladamantane-1-carboxamide Chemical compound C1C(C2)CC(C3)CC2CC13C(=O)NC1CC1 UBCVRGSRJOQNPT-UHFFFAOYSA-N 0.000 description 2
- FKTMOXNNNGGAIW-UHFFFAOYSA-N n-cyclopropylbenzenecarbothioamide Chemical compound C=1C=CC=CC=1C(=S)NC1CC1 FKTMOXNNNGGAIW-UHFFFAOYSA-N 0.000 description 2
- SMGOKOAYEGQJLG-UHFFFAOYSA-N n-cyclopropylfuran-2-carboxamide Chemical compound C=1C=COC=1C(=O)NC1CC1 SMGOKOAYEGQJLG-UHFFFAOYSA-N 0.000 description 2
- BLZTZXANILMOFM-UHFFFAOYSA-N n-cyclopropylnaphthalene-2-carboxamide Chemical compound C=1C=C2C=CC=CC2=CC=1C(=O)NC1CC1 BLZTZXANILMOFM-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005885 boration reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method for ring-opening boronation of cyclopropane compounds without metal catalysis, which comprises the steps of mixing and heating the cyclopropane compounds, naphthol borane and an organic solvent in a protective atmosphere to carry out boronation reaction, and stirring triethylamine and pinacol for 1 hour at room temperature to obtain boron-containing compounds. The method has the advantages of low production cost, simple and convenient reaction condition operation, suitability for industrial production, good chemical selectivity of the synthesized saturated borate compound, high functional group tolerance and contribution to product separation and purification.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a reaction method for ring-opening boronation of cyclopropane compounds under the condition of no metal catalysis.
Background
The cyclopropane structure of the cyclopropane compound has great potential utilization value in drug derivation and modification, and attracts numerous scientists to conduct modification exploration in recent years, wherein the realization of carbon-carbon bond activation and breaking of the cyclopropane compound to obtain a corresponding functionalized structure product is a great research hotspot in a short period of time.
Although great progress is made in activating carbon-carbon bonds of cyclopropane compounds by transition metal catalysis, noble metals such as rhodium, iridium and the like, organic phosphine and nitrogen ligands are generally used in transition metal catalysis reaction systems, so that the reaction cost and the post-treatment cost are increased, metal residue pollution problems of different degrees are generated in the noble metal catalysis reaction systems, the atom economy is poor, the environment is not green, products of carbon-hydrogen bond activation and products of different carbon-carbon bond breakage generally exist in the reaction, and the chemical selectivity and the position selectivity are also challenged, so that a reaction system with lower reaction cost is also required to be developed to solve the problems.
Disclosure of Invention
The invention aims to solve the technical problem of providing a low-cost and convenient-to-operate ring-opening boronization reaction method for cyclopropane compounds under the condition of no metal catalysis.
In order to solve the problems, the invention provides a method for ring-opening boronation of cyclopropane compounds under the catalysis of no metal, which is characterized by comprising the following steps: the method comprises the steps of mixing and heating cyclopropane compounds, naphthol borane and organic solvents in protective atmosphere to carry out boronization reaction, and stirring triethylamine and pinacol for 1 hour at room temperature to obtain boron-containing compounds.
The mol ratio of the cyclopropane compound, the naphthol borane and the pinacol is 1: (1.2 to 3.0): (1.2 to 3.0); the molar ratio of the triethylamine to the pinacol is 1:1.
the structural formula of the cyclopropane compound is shown as follows:
wherein: r is 1 Is one of aryl, aromatic heterocycle or alkyl, R 2 And R 3 Independently is one of aryl, alkyl or hydrogen, and X is oxygen or sulfur.
R 1 Is one of beta-naphthalene, aromatic heterocycle, phenyl, substituted phenyl or alkyl; said R is 2 Is one of phenyl, alkyl or hydrogen; the R is 3 Is one of phenyl, substituted phenyl or hydrogen; the substituent in the substituted phenyl is one of methyl, fluorine, chlorine, bromine, tertiary butyl, phenyl, trifluoromethyl, cyano, ester group, N-dimethyl, acetyl, nitro or methoxyl.
The organic solvent is one of toluene, tetrahydrofuran, p-xylene, 1,4-dioxane, 1,2-dichloroethane, diethylene glycol dimethyl ether or methyl tert-butyl ether.
The boronizing reaction conditions are that the temperature is 100 to 150 ℃ and the time is 6 to 48h.
The protective atmosphere is nitrogen atmosphere or argon atmosphere.
Compared with the prior art, the invention has the following advantages:
1. the invention uses the mixture of naphthol borane and cyclopropane compound to heat under the condition of no metal catalysis, so as to realize the selective boronization reaction of carbon-carbon bond activation ring opening, and prepare the cyclopropane saturated straight-chain ring opening monoboron compound.
2. The method only uses the secondary naphthol borane as the boronizing reagent, does not need transition metal catalysis, improves the reaction economy, has good atom economy, and meets the requirement of green chemistry.
3. The invention has the advantages of cheap and easily obtained raw materials, low production cost, simple and convenient reaction condition operation and suitability for industrial production.
4. The saturated borate compound synthesized by the method has good chemical selectivity and high functional group tolerance, and is beneficial to separation and purification of products.
Detailed Description
A reaction method for ring-opening boronization of cyclopropane compounds without metal catalysis is characterized in that the cyclopropane compounds, the naphthol borane and an organic solvent are mixed and heated in a protective atmosphere to carry out boronization reaction; and stirring the mixture for 1 hour at room temperature by using triethylamine and pinacol to obtain the boron-containing compound.
The reaction equation is as follows:
wherein: the mol ratio of the cyclopropane compound, the naphthol borane and the pinacol is 1: (1.2 to 3.0): (1.2 to 3.0).
The molar ratio of cyclopropane compound to naphthol borane is preferably 1: (1.5 to 3.0), most preferably 1: (1.7 to 2.5).
The molar ratio of triethylamine to pinacol is 1:1.
in the present invention, the ratio of the molar amount of the cyclopropane compound to the volume of the organic solvent is preferably (0.2 to 0.3) mmol: (0.5 to 3) mL.
The structural formula of the cyclopropane compound is shown as follows:
wherein: r 1 Is one of aryl, aromatic heterocycle or alkyl, R 2 And R 3 Independently one of aryl, alkyl or hydrogen, and X is oxygen or sulfur.
Preferably: r 1 Is one of beta-naphthalene, aromatic heterocycle, phenyl, substituted phenyl or alkyl; r 2 Is one of phenyl, alkyl or hydrogen; r 3 Is one of phenyl, substituted phenyl or hydrogen; the substituent in the substituted phenyl is one of methyl, fluorine, chlorine, bromine, tertiary butyl, phenyl, trifluoromethyl, cyano, ester group, N-dimethyl, acetyl, nitro or methoxyl. The present invention is not limited to any particular substitution site for the substituent.
In a specific embodiment of the present invention, the cyclopropane compound is N-cyclopropylbenzamide, N-cyclopropyl-4-methylbenzamide, N-cyclopropyl-4-tert-butylbenzamide, N-cyclopropyl-4-methoxybenzamide, N-cyclopropyl-4-phenylbenzamide, N-cyclopropyl-4-N, N-dimethylbenzamide, N-cyclopropyl-4-fluorobenzamide, N-cyclopropyl-4-chlorobenzamide, N-cyclopropyl-4-bromobenzamide, N-cyclopropyl-4-trifluoromethylbenzamide, N-cyclopropyl-4-acetylbenzamide, N-cyclopropyl-4-carbomethoxybenzamide, N-cyclopropyl-4-nitrobenzamide, N-cyclopropyl-4-cyanobenzamide, N-cyclopropyl- β -naphthamide, N-cyclopropyl-pentafluorobenzamide, N-cyclopropyl-4-diphenylphosphinobenzamide, N-cyclopropyl-2-methylbenzamide, N-cyclopropyl-2-chlorobenzamide, N-cyclopropyl-3-methylbenzamide, N-cyclopropyl-3-chlorobenzamide, N-cyclopropyl-2-furancarboxamide, N-cyclopropyl-2-thiophenecarboxamide, N-cyclopropyl-benzo [ 8978 xzft ] 5-carboxamide, N-cyclopropyl-2-thiophenecarboxamide, N-cyclopropyl-benzo [ 8978 x ] dioxolane 8978, N-cyclopropyl-2-ferrocenecarboxamide, N- (1-methylcyclopropyl) -benzamide, N- (1-phenylcyclopropyl) -benzamide, N- (1- (2-cyclopentylvinyl) cyclopropyl) -benzamide, N- (1-methylcyclopropyl) -benzamide, N- (2-phenylcyclopropyl) -benzamide, N- (2- (3,4-difluorophenyl) cyclopropyl) -benzamide, N-cyclopropyl-1-methylcyclohexyl-1-carboxamide, N-cyclopropyl-1-adamantylcarboxamide, N-cyclopropyl-1-cyclohexenyl-1-carboxamide, N-cyclopropylpivaloamide, N- (1- (2-cyclopentylvinyl) cyclopropyl) -pivaloamide, N-cyclopropylthiopivaloamide or N-cyclopropylthiobenzamide.
The organic solvent is one of toluene, tetrahydrofuran, p-xylene, 1,4-dioxane, 1,2-dichloroethane, diethylene glycol dimethyl ether or methyl tert-butyl ether. Preferably: toluene, tetrahydrofuran, p-xylene, 1,4-dioxane or diethylene glycol dimethyl ether.
In the present invention, the mixing is preferably performed by mixing cyclopropane compounds, naphthol borane and organic solvents, heating, cooling to room temperature after the reaction is completed, adding triethylamine and pinacol in an inert gas atmosphere, and then stirring at room temperature for one hour. The addition mode of the cyclopropane compound, the naphthol borane and the organic solvent is not limited in any way, and the method is well known to those skilled in the art.
In the present invention, the protective atmosphere is a nitrogen atmosphere or an argon atmosphere. The pressure of the protective atmosphere is preferably 1atm; the temperature of the boronation reaction is preferably 100 to 150 ℃, and the time of the boronation reaction is preferably 6 to 48h, more preferably 10 to 36h, and most preferably 12 to 24h. In the present invention, the boronation reaction is preferably carried out under stirring, and the stirring conditions are not particularly limited, and may be carried out by a method known to those skilled in the art.
After the boration reaction is completed, the present invention preferably further comprises separation, and the separation is carried out by column chromatography and reduced pressure spin-drying, which are well known to those skilled in the art, without any particular limitation. In the embodiment of the present invention, in the embodiments 1 to 19, a product system containing a saturated monoboron compound is directly obtained without separation, and the yield of the saturated monoboron compound in the product system is detected by a gas phase. If the product system needs to be separated and purified, the separation method is referred to.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
Example 1
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (1 mL), and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 140 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound represented by formula 2 a. The yield was 83% by GC.
The chemical reaction formula of the preparation process is as follows:
example 2
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), tetrahydrofuran (1 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 140 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound represented by formula 2 a. The yield was 61% by GC.
The chemical reaction formula of the preparation process is as follows:
example 3
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), 1,4-dioxane (1 mL), and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) and stirred at 140 ℃ for 12h, after which triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to give a product system containing the compound of formula 2 a. The yield was 82% by GC.
The chemical reaction formula of the preparation process is as follows:
example 4
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), p-xylene (1 mL), and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 140 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound represented by formula 2 a. The yield was 71% by GC.
The chemical reaction formula of the preparation process is as follows:
example 5
Naphtholborane (HBcat, 0.4mmol, 42.7. Mu.L), methyl tert-butyl ether (1 mL) and N-cyclopropylbenzamide (1a, 0.2mmol,32.2 mg) were mixed under a nitrogen atmosphere (1 atm), and stirred at 140 ℃ for 12 hours, after which triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound represented by formula 2 a. The yield was 11% by GC.
The chemical reaction formula of the preparation process is as follows:
example 6
Naphtholborane (HBcat, 0.4mmol, 42.7. Mu.L), diethylene glycol dimethyl ether (1 mL) and N-cyclopropylbenzamide (1a, 0.2mmol,32.2 mg) were mixed under a nitrogen atmosphere (1 atm), stirred at 140 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound having the structure represented by formula 2 a. The yield was 64% by GC.
The chemical reaction formula of the preparation process is as follows:
example 7
Naphtholborane (HBcat, 0.4mmol, 42.7. Mu.L), 1,2-dichloroethane (1 mL), and N-cyclopropylbenzamide (1a, 0.2mmol,32.2 mg) were mixed under nitrogen (1 atm), stirred at 140 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound represented by formula 2 a. The yield was 83% by GC.
The chemical reaction formula of the preparation process is as follows:
example 8
Naphtholborane (HBcat, 0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropylbenzamide (1a, 0.2mmol,32.2 mg) were mixed under a nitrogen atmosphere (1 atm), and stirred at 140 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound represented by formula 2 a. The yield was 95% by GC.
The chemical reaction formula of the preparation process is as follows:
example 9
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (0.5 mL), and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under a nitrogen atmosphere (1 atm), stirred at 140 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound having the structure represented by formula 2 a. The yield was 38% by GC.
The chemical reaction formula of the preparation process is as follows:
example 10
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), 1,4-dioxane (2 mL), and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) and stirred at 140 ℃ for 12h, then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound of formula 2 a. The yield was 91% by GC.
The chemical reaction formula of the preparation process is as follows:
example 11
Naphtholborane (HBcat, 0.4mmol, 42.7. Mu.L), 1,4-dioxane (0.5 mL), and N-cyclopropylbenzamide (1a, 0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) and stirred at 140 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound having the structure represented by formula 2 a. The yield was 39% by GC.
The chemical reaction formula of the preparation process is as follows:
example 12
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), 1,4-dioxane (2 mL), and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) and stirred at 120 ℃ for 12h, then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound of formula 2 a. The yield was 91% by GC.
The chemical reaction formula of the preparation process is as follows:
example 13
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), 1,4-dioxane (2 mL), and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) and stirred at 100 ℃ for 12 hours, then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound having the structure represented by formula 2 a. The yield was 70% by GC.
The chemical reaction formula of the preparation process is as follows:
example 14
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound represented by formula 2 a. The yield was 95% by GC.
The chemical reaction formula of the preparation process is as follows:
example 15
Naphtholborane (HBcat, 0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropylbenzamide (1a, 0.2mmol,32.2 mg) were mixed under a nitrogen atmosphere (1 atm), and stirred at 100 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound represented by formula 2 a. The yield was 72% by GC.
The chemical reaction formula of the preparation process is as follows:
example 16
Naphtholborane (designated as HBcat,0.24mmol, 25.6. Mu.L), toluene (2 mL), and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under a nitrogen (1 atm) atmosphere, and stirred at 120 ℃ for 12 hours, after which triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound represented by the formula 2 a. The yield was 78% by GC.
The chemical reaction formula of the preparation process is as follows:
example 17
Naphtholborane (described as HBcat,0.3mmol, 32.0. Mu.L), toluene (2 mL), and N-cyclopropylbenzamide (described as 1a,0.2mmol,32.2 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing a compound having a structure represented by formula 2 a. The yield was 86% by GC.
The chemical reaction formula of the preparation process is as follows:
example 18
Naphtholborane (shown as HBcat,0.35mmol, 37.3. Mu.L), toluene (2 mL) and N-cyclopropylbenzamide (shown as 1a,0.2mmol,32.2 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound having the structure represented by formula 2 a. The yield was 95% by GC.
The chemical reaction formula of the preparation process is as follows:
example 19
Naphtholborane (described as HBcat,0.6mmol, 64.1. Mu.L), toluene (2 mL), and N-cyclopropylbenzamide (described as 1a,0.2mmol,32.2 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound represented by formula 2 a. The yield was 65% by GC.
The chemical reaction formula of the preparation process is as follows:
the N- (3-pinacolboronic acid ester propyl) benzamide with the structure shown in the formula 2a prepared in the examples 1 to 19 is yellow liquid, and the characterization data are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.80 – 7.74 (m, 2H), 7.50 – 7.45 (m, 1H), 7.44 – 7.38 (m, 2H), 6.48 (s, 1H), 3.44 (td, J= 6.9, 5.5 Hz, 2H), 1.74 (p, J = 7.2 Hz, 2H), 1.22 (s, 12H), 0.89 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.7, 135.1, 131.3, 128.5, 127.0, 83.5, 42.3, 24.9, 23.7. 11 B NMR (128 MHz, Chloroform-d) δ 34.36。
example 20
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-4-methylbenzamide (designated as 1b,0.2mmol,35.0 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing a compound having a structure represented by formula 2 b. The product was then purified by silica gel column chromatography with dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.66 (d, J = 8.1 Hz, 2H), 7.20 (d, J = 7.9 Hz, 2H), 6.43 (s, 1H), 3.43 (td, J = 6.9, 5.4 Hz, 2H), 2.38 (s, 3H), 1.73 (p, J = 7.1 Hz, 2H), 1.23 (s, 12H), 0.88 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.6, 141.6, 132.2, 129.2, 127.0, 83.4, 42.2, 24.9, 23.8, 21.5. 11 B NMR (128 MHz, Chloroform-d) δ 34.41。
example 21
Naphtholborane (denoted as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-4-tert-butylbenzamide (denoted as 1c,0.2mmol,43.4 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound of formula 2 c. The product was then purified by silica gel column chromatography with dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.72 – 7.66 (m, 2H), 7.45 – 7.38 (m, 2H), 6.43 (s, 1H), 3.43 (td, J = 6.9, 5.5 Hz, 2H), 1.72 (p, J = 7.3 Hz, 2H), 1.32 (s, 9H), 1.22 (s, 12H), 0.87 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.6, 154.7, 132.2, 126.8, 125.4, 83.4, 42.1, 34.9, 31.3, 24.9, 23.8. 11 B NMR (128 MHz, Chloroform-d) δ 34.25。
example 22
Naphtholborane (denoted as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-4-methoxybenzamide (denoted as 1d,0.2mmol,38.2 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing a compound having a structure represented by formula 2 d. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.77 – 7.69 (m, 2H), 6.94 – 6.86 (m, 2H), 6.38 (s, 1H), 3.84 (s, 3H), 3.42 (td, J = 6.9, 5.4 Hz, 2H), 1.79 – 1.68 (m, 2H), 1.23 (s, 12H), 0.88 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.2, 162.1, 128.8, 127.4, 113.7, 83.4, 55.5, 42.2, 24.9, 23.8. 11 B NMR (128 MHz, Chloroform-d) δ 34.06。
example 23
Naphtholborane (denoted as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-4-phenylbenzamide (denoted as 1e,0.2mmol,47.4 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound represented by formula 2 e. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15: 1) as an eluent, the solvent was spin-dried under reduced pressure to give the compound represented by the formula 2e as a white solid in an isolated yield of 50%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.87 – 7.81 (m, 2H), 7.66 – 7.51 (m, 4H), 7.49 – 7.42 (m, 2H), 7.40 – 7.34 (m, 1H), 6.61 (t, J = 5.5 Hz, 1H), 3.46 (td, J = 6.9, 5.4 Hz, 2H), 1.76 (p, J = 7.2 Hz, 2H), 1.23 (s, 12H), 0.90 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.3, 144.1, 140.2, 133.7, 128.9, 128.0, 127.5, 127.2, 127.2, 83.4, 42.3, 24.9, 23.7. 11 B NMR (128 MHz, Chloroform-d) δ 34.23。
example 24
Naphtholborane (HBcat, 0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-4-N, N-dimethylbenzamide (1f, 0.2mmol, 40.8mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing a compound having a structure represented by formula 2 f. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.70 – 7.62 (m, 2H), 6.69 – 6.61 (m, 2H), 6.24 (s, 1H), 3.41 (td, J = 7.0, 5.5 Hz, 2H), 3.00 (s, 6H), 1.78 – 1.70 (m, 2H), 1.24 (s, 12H), 0.87 (t, J = 7.7 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.4, 152.3, 128.3, 121.8, 111.0, 83.2, 41.9, 40.1, 24.8, 23.8. 11 B NMR (128 MHz, Chloroform-d) δ 33.98。
example 25
Naphtholborane (described as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-4-fluorobenzamide (described as 1g,0.2mmol,35.8 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound of the structure represented by formula 2 g. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.81 – 7.73 (m, 2H), 7.11 – 7.03 (m, 2H), 6.53 (s, 1H), 3.41 (td, J = 6.8, 5.4 Hz, 2H), 1.72 (p, J = 7.2 Hz, 2H), 1.21 (s, 12H), 0.87 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.6, 165.9, 163.4, 131.3, 131.2, 129.3, 129.2, 115.6, 115.4, 83.4, 42.3, 24.9, 23.6. 11 B NMR (128 MHz, Chloroform-d) δ 34.15. 19 F NMR (376 MHz, Chloroform-d) δ -108.82 (ddd, J = 13.7, 8.5, 5.2 Hz)。
example 26
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-4-chlorobenzamide (designated as 1h,0.2mmol,39.0 mg) were mixed under a nitrogen atmosphere (1 atm), stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing a compound having a structure represented by formula 2 h. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.74 – 7.64 (m, 2H), 7.42 – 7.31 (m, 2H), 6.50 (s, 1H), 3.43 (td, J = 6.8, 5.4 Hz, 2H), 1.74 (p, J = 7.3 Hz, 2H), 1.23 (s, 12H), 0.88 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.5, 137.5, 133.5, 128.8, 128.5, 83.5, 42.3, 24.9, 23.6. 11 B NMR (128 MHz, Chloroform-d) δ 34.43。
example 27
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-4-bromobenzamide (designated as 1i,0.2mmol,47.8 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing a compound having a structure represented by formula 2 i. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.66 – 7.60 (m, 2H), 7.56 – 7.49 (m, 2H), 6.60 (t, J = 5.5 Hz, 1H), 3.41 (td, J = 6.9, 5.4 Hz, 2H), 1.72 (p, J = 7.2 Hz, 2H), 1.21 (s, 12H), 0.87 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.6, 133.8, 131.7, 128.7, 125.9, 83.4, 42.3, 24.9, 23.5. 11 B NMR (128 MHz, Chloroform-d) δ 33.63。
example 28
Naphtholborane (described as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-4-trifluoromethylbenzamide (described as 1j,0.2mmol,45.8 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing a compound having a structure represented by formula 2 j. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
characterization dataComprises the following steps: 1 H NMR (400 MHz, Chloroform-d) δ 7.87 (d, J = 7.8 Hz, 2H), 7.66 (d, J = 8.1 Hz, 2H), 6.70 (s, 1H), 3.44 (td, J = 6.8, 5.4 Hz, 2H), 1.74 (p, J = 7.2 Hz, 2H), 1.21 (s, 12H), 0.88 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.4, 138.4, 133.2, 132.9, 127.5, 125.5 (q, J = 3.8 Hz), 83.5, 42.4, 24.8, 23.5. 11 B NMR (128 MHz, Chloroform-d) δ 34.09. 19 F NMR (376 MHz, Chloroform-d) δ -62.92。
example 29
Naphtholborane (HBcat, 0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-acetylbenzamide (1k, 0.2mmol,40.6 mg) were mixed under a nitrogen atmosphere (1 atm), stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound represented by formula 2 k. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (8:1 by volume) as eluent, the solvent was spin-dried under reduced pressure to give the compound of formula 2k as a colorless liquid with an isolation yield of 35%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 8.03 – 7.96 (m, 2H), 7.89 – 7.78 (m, 2H), 6.61 (s, 1H), 3.46 (td, J = 6.8, 5.4 Hz, 2H), 2.63 (s, 3H), 1.76 (p, J = 7.2 Hz, 2H), 1.23 (s, 12H), 0.93 – 0.88 (m, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 197.6, 166.6, 139.1, 139.0, 128.5, 127.4, 83.5, 42.4, 26.9, 24.9, 23.5. 11 B NMR (128 MHz, Chloroform-d) δ 34.01。
example 30
Naphtholborane (described as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-4-carboxymethylbenzamide (described as 1l,0.2mmol,43.8 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound represented by formula 2L. The product was then purified by silica gel column chromatography with dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 8.13 – 7.99 (m, 2H), 7.84 – 7.77 (m, 2H), 6.77 (s, 1H), 3.91 (s, 3H), 3.42 (td, J = 6.8, 5.4 Hz, 2H), 1.72 (p, J = 7.2 Hz, 2H), 1.19 (s, 12H), 0.87 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.7, 166.4, 139.0, 132.5, 129.7, 127.1, 83.4, 52.4, 42.4, 24.8, 23.5. 11 B NMR (128 MHz, Chloroform-d) δ 33.57。
example 31
Naphtholborane (HBcat, 0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-4-nitrobenzamide (1m, 0.2mmol,41.2 mg) were mixed under a nitrogen atmosphere (1 atm), and stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the structural compound represented by formula 2 m. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 10).
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 8.29 – 8.22 (m, 2H), 7.97 – 7.90 (m, 2H), 6.82 (s, 1H), 3.45 (td, J = 6.8, 5.4 Hz, 2H), 1.75 (p, J = 7.1 Hz, 2H), 1.22 (s, 12H), 0.89 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 165.5, 149.5, 140.7, 128.2, 123.8, 83.5, 42.6, 24.9, 23.4. 11 B NMR (128 MHz, Chloroform-d) δ 34.18。
example 32
Naphtholborane (HBcat, 0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-4-cyanobenzamide (1n, 0.2mmol,39.2 mg) were mixed under a nitrogen atmosphere (1 atm), stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the structural compound represented by formula 2N. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.92 – 7.81 (m, 2H), 7.76 – 7.69 (m, 2H), 6.72 (s, 1H), 3.46 (td, J = 6.8, 5.4 Hz, 2H), 1.75 (q, J = 7.1 Hz, 2H), 1.23 (s, 12H), 0.90 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 165.8, 139.0, 132.4, 127.8, 118.2, 114.9, 83.5, 42.5, 24.9, 23.4. 11 B NMR (128 MHz, Chloroform-d) δ 34.39。
example 33
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-beta-naphthamide (designated as 1o,0.2mmol,42.2 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing a compound having a structure represented by formula 2 o. The product was then purified by silica gel column chromatography with dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 8.28 (s, 1H), 7.87 (ddt, J = 13.4, 10.3, 6.6 Hz, 4H), 7.60 – 7.48 (m, 2H), 6.63 (s, 1H), 3.51 (td, J = 6.9, 5.4 Hz, 2H), 1.79 (p, J = 7.2 Hz, 2H), 1.23 (s, 12H), 0.93 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.7, 134.8, 132.8, 132.4, 128.4, 127.8, 127.6, 127.4, 126.8, 123.8, 83.4, 42.4, 24.9, 23.8. 11 B NMR (128 MHz, Chloroform-d) δ 34.48。
example 34
Naphtholborane (denoted as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-pentafluorobenzamide (denoted as 1p,0.2mmol,50.0 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing a compound represented by the formula 2 p. The product was then purified by silica gel column chromatography with dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 6.46 (s, 1H), 3.38 (td, J= 6.8, 5.5 Hz, 2H), 1.70 – 1.61 (m, 2H), 1.15 (s, 12H), 0.81 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 157.1, 145.3, 119.5, 118.6, 117.0, 83.4, 42.4, 24.7, 23.1. 11 B NMR (128 MHz, Chloroform-d) δ 33.95. 19 F NMR (376 MHz, Chloroform-d) δ -140.28 – -140.52 (m), -151.30 (tt, J = 20.7, 3.0 Hz), -160.12 – -160.48 (m)。
example 35
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-4-diphenylphosphinobenzamide (designated as 1q,0.2mmol,69.0 mg) were mixed under a nitrogen gas (1 atm) atmosphere, stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing a compound represented by the formula 2 q. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.74 – 7.67 (m, 2H), 7.40 – 7.25 (m, 12H), 6.47 (s, 1H), 3.44 (td, J = 6.9, 5.5 Hz, 2H), 1.73 (p, J = 7.2 Hz, 2H), 1.21 (s, 12H), 0.89 – 0.85 (m, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.4, 141.7, 136.6, 136.5, 135.2, 134.0, 133.8, 133.7, 133.5, 129.1, 128.8, 128.7, 126.9, 126.9, 83.4, 42.3, 24.9, 23.7. 11 B NMR (128 MHz, Chloroform-d) δ 34.48. 31 P NMR (162 MHz, Chloroform-d) δ -5.61。
example 36
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-2-methylbenzamide (designated as 1r,0.2mmol,35.0 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 150 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing a compound having a structure represented by formula 2 r. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.38 – 7.26 (m, 2H), 7.21 – 7.09 (m, 2H), 6.12 (s, 1H), 3.43 (td, J = 6.8, 5.5 Hz, 2H), 2.44 (s, 3H), 1.73 (p, J = 7.2 Hz, 2H), 1.19 (s, 12H), 0.88 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 170.1, 136.9, 135.9, 130.8, 129.6, 126.6, 125.6, 83.3, 41.9, 24.7, 23.6, 19.7. 11 B NMR (128 MHz, Chloroform-d) δ 34.28。
example 37
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-2-chlorobenzamide (designated as 1s,0.2mmol,39.0 mg) were mixed under a nitrogen atmosphere (1 atm), stirred at 150 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing a compound having a structure represented by formula 2 s. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.65 – 7.56 (m, 1H), 7.45 – 7.24 (m, 3H), 6.47 (s, 1H), 3.45 (td, J = 6.9, 5.5 Hz, 2H), 1.74 (p, J = 7.2 Hz, 2H), 1.19 (s, 12H), 0.88 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.6, 135.8, 131.1, 130.7, 130.2, 130.1, 127.1, 83.4, 42.3, 24.8, 23.6. 11 B NMR (128 MHz, Chloroform-d) δ 34.13。
example 38
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-3-methylbenzamide (designated as 1t,0.2mmol,35.0 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing a compound having the structure represented by formula 2 t. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.58 (s, 1H), 7.52 (dq, J= 5.7, 1.9 Hz, 1H), 7.33 – 7.24 (m, 2H), 6.43 (s, 1H), 3.43 (td, J = 6.9, 5.5 Hz, 2H), 2.38 (s, 3H), 1.73 (p, J = 7.7, 7.3 Hz, 3H), 1.22 (s, 12H), 0.88 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.8, 138.2, 135.0, 131.9, 128.2, 127.6, 123.8, 83.3, 42.1, 24.7, 23.6, 21.3. 11 B NMR (128 MHz, Chloroform-d) δ 34.04。
example 39
Naphtholborane (HBcat, 0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-3-chlorobenzamide (1u, 0.2mmol,39.0 mg) were mixed under a nitrogen atmosphere (1 atm), and stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound having the structure represented by formula 2 u. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.73 (t, J = 1.9 Hz, 1H), 7.63 (dt, J = 7.6, 1.4 Hz, 1H), 7.43 (ddd, J = 8.0, 2.1, 1.1 Hz, 1H), 7.33 (t, J = 7.9 Hz, 1H), 6.63 (s, 1H), 3.42 (td, J = 6.8, 5.4 Hz, 2H), 1.73 (p, J= 7.2 Hz, 2H), 1.21 (s, 12H), 0.87 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.3, 137.0, 134.7, 131.3, 129.8, 127.3, 125.2, 83.5, 42.4, 24.9, 23.5. 11 B NMR (128 MHz, Chloroform-d) δ 34.09。
example 40
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-2-furancarboxamide (designated as 1v,0.2mmol,31.0 mg) were mixed under a nitrogen atmosphere (1 atm), stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing a compound having a structure represented by formula 2 v. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.40 (dd, J = 1.8, 0.8 Hz, 1H), 7.08 (dd, J = 3.5, 0.8 Hz, 1H), 6.56 (s, 1H), 6.47 (dd, J = 3.5, 1.8 Hz, 1H), 3.40 (td, J = 7.0, 5.8 Hz, 2H), 1.77 – 1.67 (m, 2H), 1.24 (s, 12H), 0.86 (t, J = 7.7 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 158.5, 148.4, 143.6, 113.9, 112.2, 83.3, 41.3, 24.9, 24.0. 11 B NMR (128 MHz, Chloroform-d) δ 34.26。
example 41
Naphtholborane (noted as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-2-thiophenecarboxamide (noted as 1w,0.2mmol,33.4 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound of the structure represented by formula 2 w. The product was then purified by silica gel column chromatography with dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.48 (dd, J = 3.7, 1.2 Hz, 1H), 7.42 (dd, J = 5.0, 1.2 Hz, 1H), 7.03 (dd, J = 5.0, 3.7 Hz, 1H), 6.37 (s, 1H), 3.39 (td, J = 7.0, 5.6 Hz, 2H), 1.71 (p, J = 7.4 Hz, 2H), 1.22 (s, 12H), 0.85 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 161.9, 139.3, 129.5, 127.7, 127.4, 83.3, 42.0, 24.7, 23.7. 11 B NMR (128 MHz, Chloroform-d) δ 34.05。
example 42
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-benzo [1,3-dioxolane ] 5-carboxamide (designated as 1x,0.2mmol,41.0 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing a compound having a structure represented by formula 2 x. The product was then purified by silica gel column chromatography with dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.33 – 7.23 (m, 2H), 6.81 (d, J = 8.0 Hz, 1H), 6.42 (s, 1H), 6.01 (s, 2H), 3.41 (td, J = 6.9, 5.4 Hz, 2H), 1.73 (p, J = 7.2 Hz, 2H), 1.24 (s, 12H), 0.88 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.9, 150.2, 147.9, 129.3, 121.5, 108.0, 107.7, 101.7, 83.4, 42.3, 24.9, 23.6. 11 B NMR (128 MHz, Chloroform-d) δ 34.09。
example 43
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-2-ferrocenecarboxamide (designated as 1y,0.2mmol,53.8 mg) were mixed under a nitrogen atmosphere (1 atm), stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing a compound having a structure represented by formula 2 y. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 5.88 (s, 1H), 4.64 (s, 2H), 4.31 (s, 2H), 4.19 (s, 5H), 3.35 (q, J = 6.7 Hz, 2H), 1.69 (p, J = 7.5 Hz, 2H), 1.25 (s, 12H), 0.86 (t, J = 7.8 Hz, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 170.2, 83.3, 70.3, 69.8, 68.1, 41.7, 24.9, 24.2. 11 B NMR (128 MHz, Chloroform-d) δ 34.46。
example 44
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N- (1-methylcyclopropyl) -benzamide (designated as 1z,0.2mmol,35.0 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing a compound having a structure represented by formula 2 z. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.78 – 7.70 (m, 2H), 7.48 – 7.35 (m, 3H), 6.22 (d, J = 8.1 Hz, 1H), 4.11 (ddd, J = 14.0, 8.0, 6.6 Hz, 1H), 1.72 – 1.60 (m, 2H), 1.21 (d, J = 6.6 Hz, 3H), 1.19 (s, 12H), 0.89 – 0.82 (m, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.1, 135.3, 131.2, 128.5, 127.0, 83.3, 47.6, 30.6, 24.9, 24.7, 20.8. 11 B NMR (128 MHz, Chloroform-d) δ 34.10。
example 45
Naphtholborane (noted as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N- (1-phenylcyclopropyl) -benzamide (noted as 1aa,0.2mmol,47.4 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound represented by formula 2 aa. The product was then purified by silica gel column chromatography with dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.82 – 7.74 (m, 2H), 7.51 – 7.23 (m, 8H), 6.77 (d, J = 7.8 Hz, 1H), 5.11 (q, J = 7.4 Hz, 1H), 2.04 – 1.97 (m, 2H), 1.20 (s, 12H), 0.91 – 0.81 (m, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.0, 142.6, 135.0, 131.5, 128.7, 128.6, 127.3, 127.1, 126.6, 83.5, 55.9, 30.6, 25.0, 24.7. 11 B NMR (128 MHz, Chloroform-d) δ 33.95。
example 46
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N- (1-phenylcyclopropyl) -benzamide (designated as 1aa,0.2mmol,47.4 mg) were mixed under a nitrogen atmosphere (1 atm), stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound having the structure represented by formula 2 aa. The product was then purified by silica gel column chromatography with dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.82 – 7.74 (m, 2H), 7.51 – 7.23 (m, 8H), 6.77 (d, J = 7.8 Hz, 1H), 5.11 (q, J = 7.4 Hz, 1H), 2.04 – 1.97 (m, 2H), 1.20 (s, 12H), 0.91 – 0.81 (m, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.0, 142.6, 135.0, 131.5, 128.7, 128.6, 127.3, 127.1, 126.6, 83.5, 55.9, 30.6, 25.0, 24.7. 11 B NMR (128 MHz, Chloroform-d) δ 33.95。
example 47
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N- (1- (2-cyclopentylvinyl) cyclopropyl) -benzamide (designated as 1ab,0.2mmol,51.0 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing a compound having the structure represented by formula 2 ab. The product was then purified by silica gel column chromatography with dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.80 – 7.71 (m, 2H), 7.51 – 7.34 (m, 3H), 6.16 (d, J = 7.9 Hz, 1H), 5.44 (q, J = 10.0 Hz, 1H), 5.19 (ddd, J = 10.5, 9.2, 1.0 Hz, 1H), 4.85 (p, J = 7.6 Hz, 1H), 2.90 (h, J = 8.6 Hz, 1H), 1.92 – 1.78 (m, 1H), 1.68 – 1.52 (m, 8H), 1.21 (s, 12H), 0.94 – 0.84 (m, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.4, 138.6, 136.3, 135.1, 131.1, 128.4, 128.0, 126.9, 83.2, 52.9, 49.3, 42.9, 38.7, 33.9, 33.8, 33.0, 29.9, 29.3, 25.4, 25.4, 25.1, 24.8, 24.7, 24.6. 11 B NMR (128 MHz, Chloroform-d) δ 33.72。
example 48
Naphtholborane (noted as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N- (2-phenylcyclopropyl) -benzamide (noted as 1ac,0.2mmol,47.4 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound of formula 2 ac. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.65 – 7.58 (m, 2H), 7.49 – 7.41 (m, 1H), 7.39 – 7.27 (m, 6H), 7.24 – 7.19 (m, 1H), 6.13 (s, 1H), 3.82 (dt, J = 13.0, 6.4 Hz, 1H), 3.48 (ddd, J = 13.3, 8.4, 5.0 Hz, 1H), 3.22 – 3.14 (m, 1H), 1.28 – 1.25 (m, 2H), 1.11 (d, J = 7.5 Hz, 12H). 13 C NMR (101 MHz, Chloroform-d) δ 167.3, 144.2, 134.8, 131.2, 128.6, 128.4, 127.5, 126.8, 126.7, 83.3, 47.2, 41.1, 24.7, 24.5. 11 B NMR (128 MHz, Chloroform-d) δ 33.69。
example 49
Naphtholborane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N- (2- (3,4-difluorophenyl) cyclopropyl) -benzamide (designated 1ad,0.2mmol,54.6 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to give a product system containing a compound of the structure represented by formula 2 ad. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.64 (dd, J = 7.0, 1.6 Hz, 2H), 7.50 – 7.44 (m, 1H), 7.43 – 7.35 (m, 2H), 7.17 – 6.95 (m, 4H), 6.18 (s, 1H), 3.73 (dt, J = 13.1, 6.4 Hz, 1H), 3.49 (ddd, J = 13.6, 8.1, 5.4 Hz, 1H), 3.18 (p, J = 7.4 Hz, 1H), 1.26 (td, J = 7.1, 6.4, 3.4 Hz, 2H), 1.12 (d, J = 9.0 Hz, 12H). 13 C NMR (101 MHz, Chloroform-d) δ 167.5, 141.5, 134.7, 131.5, 128.6, 126.9, 123.5, 117.4, 117.2, 116.5, 116.4, 83.6, 47.2, 40.7, 24.8, 24.7. 11 B NMR (128 MHz, Chloroform-d) δ 33.88. 19 F NMR (376 MHz, Chloroform-d) δ -137.63, -140.83。
example 50
Naphtholborane (denoted as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-1-methylcyclohexyl-1-carboxamide (denoted as 1ae,0.2mmol, 36.2mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound represented by formula 2 ae. The product was then purified by silica gel column chromatography with dichloromethane: after elution with ethyl acetate (volume ratio 15: 1) as an eluent, the solvent was spin-dried under reduced pressure to give the compound represented by formula 2ae as a colorless liquid with an isolation yield of 66%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 5.78 (s, 1H), 3.21 (td, J= 7.2, 5.5 Hz, 2H), 1.85 (ddd, J = 12.5, 6.9, 2.5 Hz, 2H), 1.63 – 1.54 (m, 2H), 1.53 – 1.26 (m, 8H), 1.22 (s, 12H), 1.10 (s, 3H), 0.77 (t, J = 7.8 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 177.6, 83.2, 42.6, 41.5, 35.7, 25.9, 24.8, 23.9, 22.9. 11 B NMR (128 MHz, Chloroform-d) δ 34.00。
example 51
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-1-adamantylcarboxamide (designated as 1af,0.2mmol,43.8 mg) were mixed under a nitrogen gas (1 atm) atmosphere, stirred at 150 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing a structural compound represented by formula 2 af. The product was then purified by silica gel column chromatography with dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 5.73 (s, 1H), 3.21 (td, J= 7.1, 5.5 Hz, 2H), 2.05 – 2.01 (m, 3H), 1.84 (d, J = 3.0 Hz, 6H), 1.76 – 1.66 (m, 6H), 1.64 – 1.56 (m, 2H), 1.25 (s, 12H), 0.79 (t, J = 7.9 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 177.9, 83.2, 41.4, 40.6, 39.4, 36.6, 28.2, 24.9, 23.9, 8.2. 11 B NMR (128 MHz, Chloroform-d) δ 33.88。
example 52
Naphtholborane (denoted as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropyl-1-cyclohexenyl-1-carboxamide (denoted as 1ag,0.2mmol,33.0 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the compound represented by formula 2 ag. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 6.59 (tt, J = 3.8, 1.8 Hz, 1H), 5.90 (s, 1H), 3.29 (td, J = 7.0, 5.6 Hz, 2H), 2.22 (tq, J = 6.2, 2.1 Hz, 2H), 2.17 – 2.12 (m, 2H), 1.69 – 1.55 (m, 6H), 1.24 (s, 12H), 0.82 (t, J= 7.8 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 168.8, 133.6, 132.9, 83.3, 41.7, 25.4, 24.9, 24.4, 23.9, 22.3, 21.7. 11 B NMR (128 MHz, Chloroform-d) δ 33.83。
example 53
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropylpivaloamide (designated as 1ah,0.2mmol,28.2 mg) were mixed under a nitrogen atmosphere (1 atm), stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound represented by the formula 2 ah. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 5.78 (s, 1H), 3.26 – 3.14 (m, 2H), 1.59 (p, J = 7.6 Hz, 2H), 1.23 (s, 12H), 1.16 (s, 9H), 0.77 (t, J = 7.8 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 178.4, 83.3, 41.6, 38.7, 27.7, 24.9, 23.9. 11 B NMR (128 MHz, Chloroform-d) δ 34.04。
example 54
Naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N- (1- (2-cyclopentylvinyl) cyclopropyl) -pivaloamide (designated as 1ai,0.2mmol,47.0 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 120 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound having the structure represented by formula 2 ai. The product was then purified by silica gel column chromatography with dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 5.54 – 5.34 (m, 2H), 5.31 – 4.99 (m, 1H), 4.65 – 4.26 (m, 1H), 2.89 – 2.30 (m, 1H), 1.78 – 1.52 (m, 9H), 1.22 (s, 13H), 1.16 (d, J = 9.7 Hz, 9H), 0.74 (ddd, J = 9.0, 6.7, 1.8 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 177.5, 177.2, 138.7, 136.0, 128.3, 128.2, 83.2, 52.2, 48.7, 43.0, 38.7, 38.6, 34.0, 33.9, 33.1, 33.1, 30.0, 29.5, 27.7, 27.7, 25.5, 25.4, 25.1, 24.9, 24.9. 11 B NMR (128 MHz, Chloroform-d) δ 34.66。
example 55
Naphtholborane (HBcat, 0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropylthio-pivaloamide (1aj, 0.2mmol,31.4 mg) were mixed under a nitrogen atmosphere (1 atm), and stirred at 150 ℃ for 12 hours, after which triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to obtain a product system containing the structural compound represented by formula 2 aj. The product was then purified by silica gel column chromatography with dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
number of tokensAccording to the following steps: 1 H NMR (400 MHz, Chloroform-d) δ 7.53 (s, 1H), 3.63 (td, J= 7.2, 5.0 Hz, 2H), 1.83 – 1.71 (m, 2H), 1.34 (s, 9H), 1.25 (s, 12H), 0.85 (t, J = 7.8 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 213.1, 83.5, 48.7, 44.5, 30.2, 24.9, 22.3. 11 B NMR (128 MHz, Chloroform-d) δ 34.08。
example 56
Naphtholborane (denoted as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL), and N-cyclopropylthiobenzamide (denoted as 1aj,0.2mmol,35.4 mg) were mixed under a nitrogen (1 atm) atmosphere, stirred at 150 ℃ for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to obtain a product system containing the compound represented by formula 2 aj. The product was then purified by silica gel column chromatography using dichloromethane: after elution with ethyl acetate (volume ratio 15.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 8.32 (s, 1H), 7.78 – 7.71 (m, 2H), 7.56 – 7.29 (m, 3H), 3.79 (td, J = 6.6, 4.9 Hz, 2H), 1.90 (p, J = 7.0 Hz, 2H), 1.17 (s, 12H), 0.97 (t, J = 7.2 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 199.2, 142.4, 130.9, 128.5, 126.9, 83.7, 49.4, 24.8, 22.1. 11 B NMR (128 MHz, Chloroform-d) δ 34.19。
the foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A reaction method for ring-opening boronization of cyclopropane compounds under the catalysis of no metal is characterized in that: the method comprises the steps of mixing and heating cyclopropane compounds, naphthol borane and organic solvents in protective atmosphere to carry out boronization reaction, and stirring triethylamine and pinacol for 1 hour at room temperature to obtain boron-containing compounds.
2. The method for the ring-opening boronation of cyclopropane compounds without metal catalysis in claim 1, which comprises the following steps: the mol ratio of the cyclopropane compound, the naphthol borane and the pinacol is 1: (1.2 to 3.0): (1.2 to 3.0); the molar ratio of the triethylamine to the pinacol is 1:1.
3. the metal-free ring-opening boronation reaction method for cyclopropane compounds according to claim 1 or 2, which comprises: the structural formula of the cyclopropane compound is shown as follows:
wherein: r 1 Is one of aryl, aromatic heterocycle or alkyl, R 2 And R 3 Independently is one of aryl, alkyl or hydrogen, and X is oxygen or sulfur.
4. The method for the ring-opening boronation of cyclopropane compounds without metal catalysis in claim 3, which comprises the following steps: r is 1 Is one of beta-naphthalene, aromatic heterocycle, phenyl, substituted phenyl or alkyl; said R is 2 Is one of phenyl, alkyl or hydrogen; the R is 3 Is one of phenyl, substituted phenyl or hydrogen; the substituent in the substituted phenyl is one of methyl, fluorine, chlorine, bromine, tertiary butyl, phenyl, trifluoromethyl, cyano, ester group, N-dimethyl, acetyl, nitro or methoxyl.
5. The method for the ring-opening boronation of cyclopropane compounds without metal catalysis in claim 1, which comprises the following steps: the organic solvent is one of toluene, tetrahydrofuran, paraxylene, 1,4-dioxane, 1,2-dichloroethane, diethylene glycol dimethyl ether or methyl tert-butyl ether.
6. The method for the ring-opening boronation of cyclopropane compounds without metal catalysis in claim 1, which comprises the following steps: the boronation reaction condition is that the temperature is 100 to 150 ℃ and the time is 6 to 48h.
7. The method for the ring-opening boronation of cyclopropane compounds without metal catalysis in claim 1, which comprises the following steps: the protective atmosphere is nitrogen atmosphere or argon atmosphere.
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| CN114605458A (en) * | 2022-05-03 | 2022-06-10 | 上海毕得医药科技股份有限公司 | Method for preparing chiral gamma-amino boric acid ester by activating carbon-carbon bond of cyclopropane under catalysis of transition metal |
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| CN114805409B (en) * | 2022-04-13 | 2023-09-19 | 中国科学院兰州化学物理研究所 | Reaction method for ring-opening boronation of cyclopropane compound by front transition metal catalysis |
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