CN109293484B - Method for preparing deuterated aldehyde from carboxylic acid under blue light irradiation by using iridium complex as catalyst - Google Patents
Method for preparing deuterated aldehyde from carboxylic acid under blue light irradiation by using iridium complex as catalyst Download PDFInfo
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- CN109293484B CN109293484B CN201811227050.8A CN201811227050A CN109293484B CN 109293484 B CN109293484 B CN 109293484B CN 201811227050 A CN201811227050 A CN 201811227050A CN 109293484 B CN109293484 B CN 109293484B
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- carboxylic acid
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- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 17
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title description 10
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 137
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011941 photocatalyst Substances 0.000 claims abstract description 46
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 41
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims abstract description 36
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 10
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims abstract description 9
- -1 aromatic aldehyde compound Chemical class 0.000 claims abstract description 9
- JCRCPEDXAHDCAJ-UHFFFAOYSA-N ethoxy(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(OCC)C1=CC=CC=C1 JCRCPEDXAHDCAJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 150000003384 small molecules Chemical class 0.000 claims abstract description 3
- QLPCAAJSEQIZOP-UHFFFAOYSA-N 2,4,6-tri(propan-2-yl)benzenethiol Chemical compound CC(C)C1=CC(C(C)C)=C(S)C(C(C)C)=C1 QLPCAAJSEQIZOP-UHFFFAOYSA-N 0.000 claims description 44
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 abstract description 33
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 abstract 6
- 235000019797 dipotassium phosphate Nutrition 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 101
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 87
- 238000005160 1H NMR spectroscopy Methods 0.000 description 72
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 36
- 238000004440 column chromatography Methods 0.000 description 36
- 238000011068 loading method Methods 0.000 description 36
- 239000002904 solvent Substances 0.000 description 36
- 238000005303 weighing Methods 0.000 description 36
- 239000003480 eluent Substances 0.000 description 34
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 description 34
- 238000010348 incorporation Methods 0.000 description 34
- 239000003208 petroleum Substances 0.000 description 34
- 238000001035 drying Methods 0.000 description 32
- 238000002390 rotary evaporation Methods 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000007832 Na2SO4 Substances 0.000 description 29
- 239000000203 mixture Substances 0.000 description 29
- 229910052938 sodium sulfate Inorganic materials 0.000 description 29
- 239000007789 gas Substances 0.000 description 28
- 239000012074 organic phase Substances 0.000 description 28
- 238000010898 silica gel chromatography Methods 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000004587 chromatography analysis Methods 0.000 description 13
- 239000000741 silica gel Substances 0.000 description 13
- 229910002027 silica gel Inorganic materials 0.000 description 13
- 239000003814 drug Substances 0.000 description 10
- 238000005361 D2 NMR spectroscopy Methods 0.000 description 9
- 229940079593 drug Drugs 0.000 description 9
- 229910052805 deuterium Inorganic materials 0.000 description 6
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 5
- 238000005286 illumination Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000002503 metabolic effect Effects 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- KUGCDWBFEFTQGA-UHFFFAOYSA-N C(C)(C)C1=C(C(=CC(=C1)C(C)C)C(C)C)C=1C(=CC=CC=1)S Chemical compound C(C)(C)C1=C(C(=CC(=C1)C(C)C)C(C)C)C=1C(=CC=CC=1)S KUGCDWBFEFTQGA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 150000001975 deuterium Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009509 drug development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 150000002192 fatty aldehydes Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000037353 metabolic pathway Effects 0.000 description 1
- 230000037323 metabolic rate Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
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- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing deuterated aldehyde from carboxylic acid by blue light irradiation with iridium complex as catalyst includes such steps as using aromatic carboxylic acid (ArCOOH) as raw material and triphenylphosphine as deoxidant, blue-light irradiation, solution of dichloromethane and heavy water in argon atmosphere, and potassium hydrogen phosphate as alkali3)ppy)2(dtbbpy)]PF6Is a photocatalyst, and thiophenol 2,4, 6-trisisopulbenzenethiol is an organic small molecule catalyst to obtain the deuterated aromatic aldehyde compound. Or it takes aliphatic carboxylic acid (Alk-COOD) as raw material, diphenyl ethoxy phosphine as deoxidizer and [ Ir (dF (Me) ppy)2(dtbbpy)]PF6The method is characterized in that the compound is a photocatalyst, thiophenol 2,4, 6-trisisopulbenzenethiol is an organic small molecular catalyst, and the deuterated aliphatic aldehyde compound is obtained under the irradiation of a blue light lamp, in a toluene solution and in an argon atmosphere and under the condition that 2, 6-dimethylpyridine is used as alkali.
Description
Technical Field
The invention relates to a method for preparing deuterated aldehyde from acid.
Background
Deuterium (deuterium) is a stable isotope of hydrogen with the symbol D or2H, has wide application in the fields of organic synthesis and medicinal chemistry. Deuterium is introduced into non-metabolic sites and non-action sites of drug molecules, so that the absorption, distribution, metabolism, excretion and the like of the drug molecules can be studied under the condition of not influencing the action of the drug. In particular many drugsThe C-H bond breakage is involved in the metabolism of the substance in human body, so that the deuterium atom introduced into the metabolic site of the drug can well slow or prevent the C-D bond breakage, and further achieve the purpose of changing the drug metabolic rate or metabolic pathway (Mullard, A.Nat.Rev.drug Discov.2016,15,219). Currently, deuterium-substituted drug technology is also generally considered as a simple and effective drug development model (Loh et al, Science 2017,358, 1182-1187).
Aldehydes are widely used as synthetic organic fine chemicals, such as pharmaceuticals, agrochemicals or fragrances, and various aldehydes are being produced on a small or medium scale. One of the most practical routes to aldehydes is by direct reduction of carboxylic acids, and currently, two general strategies are employed to produce aldehydes: the hydrogenation of carboxylic acids to alcohols followed by relatively mild oxidation to aldehydes; the carboxylic acid is converted to a more reactive carboxylic acid derivative such as an acid chloride, anhydride, amide or activated ester, followed by catalytic hydrogenation or reduction to the aldehyde by hydrogenation. These strategies undoubtedly exhibit poor chemoselectivity and functional group tolerance, and are harsh in reaction conditions, requiring the use of sensitive reagents, etc., and in particular the preparation of deuterated aldehydes with the above strategies is a challenge (angelw. chem. int. ed.2017,56, 7808-. The preparation method adopts a photocatalysis way with mild conditions, takes stable and easily obtained carboxylic acid as a raw material, can efficiently realize the preparation of various deuterated aldehyde compounds, and has good application in the fields of fine chemical engineering, material science and pharmacy.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing deuterated aldehyde from cheap and easily-obtained acid under mild conditions.
The synthetic route of the invention is as follows:
a process for preparing deuterated aldehyde from aromatic carboxylic acid by blue light irradiation with iridium complex as catalyst includes such steps as using aromatic carboxylic acid (ArCOOH) as raw material and triphenylphosphine as deoxidant, blue light irradiation, dichloromethane and heavy water
Solutions ofWherein the volume ratio of dichloromethane to heavy water is 1:1, rapidly stirring (1500 r/min), under argon atmosphere, under the condition of potassium dihydrogen phosphate as alkali, and using [ Ir (dF (CF)3)ppy)2(dtbbpy)]PF62,4, 6-triisopropylthiophenol (2,4, 6-trisisopulbenzenethiol) is used as an organic small molecule catalyst to obtain the deuterated aromatic aldehyde compound.
The photocatalyst [ Ir (dF (CF) ]3)ppy)2(dtbbpy)]PF6And 2,4, 6-triisopropylthiophenol (2,4, 6-trisisopulbenzenethiol) has the following structure:
the preparation method is characterized in that: the Ar group in the aromatic carboxylic acid can be various substituted aryl or heteroaryl.
The preparation method is characterized in that: the mass ratio of the aromatic carboxylic acid to the triphenylphosphine is 1: 1-2.
The preparation method is characterized by comprising the following steps: the mass ratio of the dipotassium hydrogen phosphate to the aromatic carboxylic acid is 1: 1-2.
The preparation method is characterized in that: the photocatalyst [ Ir (dF (CF) ]3)ppy)2(dtbbpy)]PF6In a molar amount of 1% of the moles of aromatic carboxylic acid; the amount of the 2,4, 6-triisopropylthiophenol catalyst used is 15 mol% of the moles of the aromatic carboxylic acid.
A method for preparing deuterated aldehyde from aliphatic carboxylic acid under the irradiation of blue light by taking an iridium complex as a catalyst,
it uses deuterated aliphatic carboxylic acid (Alk-COOD) as raw material, uses diphenyl ethoxy phosphine as deoxidant and uses [ Ir (dF (Me) ppy)2(dtbbpy)]PF6As a photocatalyst, 2,4, 6-triisopropylphenylthioPhenol (2,4, 6-trisisopulbenzenethiol) is an organic small molecular catalyst, and the deuterated aliphatic aldehyde compound is obtained under the irradiation of a blue light lamp in a toluene solution and in the presence of 2, 6-dimethylpyridine under the atmosphere of argon.
The photocatalyst [ Ir (dF (Me) ppy)2(dtbbpy)]PF6And 2,4, 6-triisopropylthiophenol catalyst have the following structures:
the preparation method is characterized in that: the fatty carboxylic acid may be a fatty carboxylic acid of various alkyl groups.
The preparation method is characterized in that: the mass ratio of the fatty carboxylic acid to the diphenyl ethoxy phosphine is 1: 1-2.
The preparation method is characterized in that: the mass ratio of the 2, 6-lutidine to the fatty carboxylic acid is 1: 1-2.
The preparation method is characterized in that: the photocatalyst [ Ir (dF (Me) ppy)2(dtbbpy)]PF6The amount used is 2.5% of the molar amount of the aliphatic carboxylic acid; the amount of the 2,4, 6-triisopropylthiophenol catalyst used is 40 mol% of the moles of the aliphatic carboxylic acid.
The method utilizes phosphine free radical chemistry through light and organic micromolecule concerted catalysis, directly takes cheap, easily-obtained and abundant carboxylic acid as a raw material and takes cheap deuterium water as a deuterium source under the steps of mild conditions and simple and convenient operation, can efficiently realize the preparation of various deuterated aldehyde compounds, and shows good chemical selectivity and functional group tolerance. Meanwhile, the method can conveniently carry out later modification on complex drug molecules and compounds, and has great significance for the research and development of deuterated drugs.
Detailed Description
The following examples are used to aid understanding of the present invention, but are not intended to limit the scope of the present invention.
Example of preparation of deuterated aromatic aldehyde:
example 1
Firstly, weighing
(39.6mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was carefully added, and then the tube was sealed and placed under irradiation of a 5W blue LED lamp (brand: Edron, model: led lamp strip, the same below) to react at room temperature for 36 hours. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing the solvent by rotary evaporation, loading by a dry method, and performing column chromatography (300-400-mesh chromatography silica gel) (eluent: petroleum ether-ethyl acetate, volume ratio: 30-15:1) to obtain the product
31.5mg, yield 86%, D incorporation by1H NMR:96％。1H NMR(400MHz,Chloroform-d)δ10.06(s,0.04H),7.96(d,J＝8.2Hz,2H),7.76(d,J＝8.2Hz,2H),7.69–7.61(m,2H),7.52–7.40(m,3H)。13C NMR(100MHz,Chloroform-d)δ191.5(t,J＝26.6Hz),147.2,139.7,135.1(t,J＝3.6Hz),130.3,129.0,128.5,127.7,127.4.2H NMR(92MHz,Chloroform-d)δ10.08(s,1D).HRMS(ESI)Calculated for C13H10DO+([M+H]+):184.0867,found:184.0869。
Example 2
Firstly, weighing
(35.6mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, via a vacuum tubeThe gas was removed by vacuum pumping three times and DCM/D was added under argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 100-50:1) to obtain product
28.7mg, 88% yield, D incorporation by1H NMR:97％.1H NMR(400MHz,Chloroform-d)δ9.98(s,0.03H),7.82(d,J＝8.6Hz,2H),7.56(d,J＝8.6Hz,2H),1.36(s,9H).13C NMR(100MHz,Chloroform-d)δ191.6(t,J＝26.6Hz),158.5,134.0(t,J＝3.5Hz),129.7,126.0,35.4,31.1.2H NMR(92MHz,Chloroform-d)δ10.04(s,1D).HRMS(ESI)Calculated for C11H14DO+([M+H]+):164.1180,found:164.1183。
Example 3
Firstly, weighing
(33mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 30-10:1) to obtain product
20.4mg, 68% yield, D incorporation by1H NMR:96％.1H NMR(400MHz,Chloroform-d)δ9.73(s,0.04H),7.74(d,J＝8.9Hz,2H),6.70(d,J＝8.9Hz,2H),3.08(s,6H).13C NMR(100MHz,Chloroform-d)δ190.2(t,J＝25.9Hz),154.4,132.0,125.0(t,J＝3.3Hz),111.0,40.1.HRMS(ESI)Calculated for C9H11DNO+([M+H]+):151.0976,found:151.0978。
Example 4 first weighing
(45.6mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. At the end of the reaction, the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 30-10:1) to obtain product
30.7mg, yield 72%, Dincorporation by1H NMR:95％.1H NMR(400MHz,Chloroform-d)δ9.89(s,0.05H),7.85(d,J＝8.8Hz,2H),7.55–7.31(m,5H),7.08(d,J＝8.8Hz,2H),5.15(s,2H).13C NMR(100MHz,Chloroform-d)δ190.4(t,J＝26.4Hz),163.8,136.0,132.0,130.0(t,J＝3.4Hz),128.8,128.4,127.5,115.2,70.3.HRMS(ESI)Calculated for C14H12DO2 +([M+H]+):214.0973,found:214.0976。
Example 5
Firstly, weighing
(33.6mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. At the end of the reaction, the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 40-10:1) to obtain product
24.8mg, 81% yield, D incorporation by1H NMR:95％.1H NMR(400MHz,Chloroform-d)δ9.89(s,0.05H),7.85(d,J＝8.8Hz,2H),7.55–7.31(m,5H),7.08(d,J＝8.8Hz,2H),5.15(s,2H).13C NMR(100MHz,Chloroform-d)δ190.4(t,J＝26.4Hz),163.8,136.0,132.0,130.0(t,J＝3.4Hz),128.8,128.4,127.5,115.2,70.3.HRMS(ESI)Calculated for C14H12DO2 +([M+H]+):214.0973,found:214.0976。
Example 6
Firstly, weighing
(47.4mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. Reaction ofAt the end, the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 30-10:1) to obtain product
40.0mg, yield 90%, D incorporation by1H NMR:96％.1H NMR(400MHz,Chloroform-d)δ9.96(s,0.04H),7.93(s,1H),7.63(d,J＝7.5Hz,1H),7.55(d,J＝8.8Hz,1H),7.44(t,J＝7.5Hz,1H),6.83(br s,1H),1.52(s,9H)。13C NMR(100MHz,Chloroform-d)δ191.8(t,J＝26.8Hz),152.7,139.4,137.0(t,J＝3.2Hz),129.7,124.2,124.1,119.3,81.1,28.3.HRMS(ESI)Calculated for C12H15DNO3 +([M+H]+):223.1187,found:223.1190。
Example 7
Firstly, weighing
(33.2mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 30-10:1) to obtain product
23.0mg, yield 76%, D incorporation by1H NMR:95％.1H NMR(400MHz,Chloroform-d)δ9.81(s,0.05H),7.55–7.38(m,1H),7.34(d,J＝1.5Hz,1H),6.93(d,J＝7.9Hz,1H),6.08(s,2H).13C NMR(100MHz,Chloroform-d)δ189.9(t,J＝26.7Hz),153.1,148.7,131.8(t,J＝3.5Hz),128.7,108.4,106.9,102.1.HRMS(ESI)Calculated for C8H6DO3 +([M+H]+):152.0452,found:152.0454。
Example 8
Firstly, weighing
(31.1mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 100-50:1) to obtain product
23.1mg, 82% yield, D incorporation by1H NMR:95％.1H NMR(400MHz,Chloroform-d)δ9.97(s,0.05H),7.75(d,J＝8.5Hz,2H),7.68(d,J＝8.5Hz,2H).13C NMR(100MHz,Chloroform-d)δ190.5(t,J＝26.9Hz),141.0,134.6(t,J＝3.7Hz),130.9,129.5.HRMS(ESI)Calculated for C7H5DClO+([M+H]+):142.0164,found:142.0166。
Example 9
Firstly, weighing
(39.9mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 100-50:1) to obtain product
32.0mg, yield 87%, D incorporation by1H NMR:95％.1H NMR(400MHz,Chloroform-d)δ9.97(s,0.05H),7.75(d,J＝8.5Hz,2H),7.68(d,J＝8.5Hz,2H).13C NMR(100MHz,Chloroform-d)δ190.7(t,J＝26.9Hz),135.0(t,J＝3.7Hz),132.5,131.0,129.8.HRMS(ESI)Calculated for C7H5DBrO+([M+H]+):185.9659,found:185.9660。
Example 10
Firstly, weighing
(49.5mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 100-50:1) to obtain product
23.7mg, yield 51%, D incorporation by1H NMR:95％.1H NMR(400MHz,Chloroform-d)δ9.95(s,0.05H),7.91(d,J＝8.4Hz,2H),7.59(d,J＝8.4Hz,2H).13C NMR(100MHz,Chloroform-d)δ191.0(t,J＝27.0Hz),138.4,135.5(t,J＝3.6Hz),130.8,102.9.HRMS(ESI)Calculated for C7H5DIO+([M+H]+):233.9521,found:233.9525。
Example 11
Firstly, weighing
(36.0mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) to obtain product
24.1mg, 73% yield, D incorporation by1H NMR:94％.1H NMR(400MHz,Chloroform-d)δ10.08(s,0.06H),8.53(s,1H),8.30(d,J＝7.8Hz,1H),8.09(d,J＝9.1Hz,1H),7.63(t,J＝7.8Hz,1H),3.96(s,3H).13C NMR(100MHz,Chloroform-d)δ190.9(t,J＝27.0Hz),166.0,136.5(t,J＝3.6Hz),135.2,133.1,131.3,131.2,129.3,52.5.HRMS(ESI)Calculated for C9H8DO3 +([M+H]+):166.0609,found:166.0610。
Example 12
Firstly, weighing
(32.8mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 40-10:1) to obtain product
22.1mg, 74% yield, D incorporation by1H NMR:96％.1H NMR(400MHz,Chloroform-d)δ10.09(s,0.04H),8.44(s,1H),8.22(d,J＝9.0Hz,1H),8.09(d,J＝9.0Hz,1H),7.66(t,J＝7.7Hz,1H),2.67(s,3H).13C NMR(100MHz,Chloroform-d)δ197.0,191.1(t,J＝26.9Hz),137.8,136.5(t,J＝3.6Hz),133.8,133.6,129.6,129.5,26.7.HRMS(ESI)Calculated for C9H8DO2 +([M+H]+):150.0660,found:150.0663。
Example 13
Firstly, weighing
(39.8mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed at 5WThe reaction is carried out for 36h at room temperature under the irradiation of blue LEDs. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing the solvent by rotary evaporation, loading the sample by a dry method, and performing column chromatography (300-400-mesh chromatography silica gel) (eluent: petroleum ether-ethyl acetate, volume ratio: 15-4:1) to obtain the product
19.5mg, yield 53%, D incorporation by1H NMR:94％.1H NMR(400MHz,CDCl3)δ10.11(s,0.06H),8.90(d,J＝1.8Hz,1H),8.66(d,J＝4.8Hz,1H),8.11(s,1H),8.00–7.92(m,2H),7.90–7.84(m,1H),7.68(t,J＝7.7Hz,1H),7.42(dd,J＝7.6,5.1Hz,1H).13C NMR(100MHz,Chloroform-d)δ191.5(t,J＝26.9Hz),149.2,148.2,138.9,137.0(t,J＝3.5Hz),135.3,134.5,133.0,129.9,129.6,128.0,123.8.2H NMR(92MHz,Chloroform-d)δ10.14(s,1D).HRMS(ESI)Calculated for C12H9DNO+([M+H]+):185.0820,found:185.0822。
Example 14
Firstly, weighing
(35.2mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg, then sealed and placed under 5W blue LEDs lamp illumination at room temperature for 36h2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 40-10:1) to obtain product
20.3mg, yield 63%, D incorporation by1H NMR:92％.1H NMR(400MHz,CDCl3)δ10.07(s,0.08H),8.22(s,1H),8.14(d,J＝7.9,1H),7.66(d,J＝7.9Hz,1H),3.91–3.15(m,2H),2.97–2.36(m,2H).13C NMR(100MHz,Chloroform-d)δ205.7,190.8(t,J＝26.8Hz),161.1,137.8,135.9(t,J＝3.5Hz),133.9,127.6,126.4,36.4,26.4.HRMS(ESI)Calculated for C10H8DO2 +([M+H]+):162.0660,found:162.0663。
Example 15
Firstly, weighing
(34.4mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 100-50:1) to obtain product
26.7mg, 85% yield, D incorporation by1H NMR:97％.1H NMR(400MHz,Chloroform-d)δ10.16(s,0.03H),8.34(s,1H),8.08–7.80(m,4H),7.72–7.50(m,2H).13C NMR(100MHz,Chloroform-d)δ191.9(t,J＝26.7Hz),136.5,134.6,134.0(t,J＝3.5Hz),132.6,129.5,129.2,129.1,128.1,127.1,122.8.2H NMR(92MHz,Chloroform-d)δ10.19(s,1D).HRMS(ESI)Calculated for C11H8DO+([M+H]+):158.0711,found:158.0714。
Example 16
Firstly, weighing
(34.4mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 100-50:1) to obtain product
28.9mg, yield 92%, D incorporation by1H NMR:95％.1H NMR(400MHz,Chloroform-d)δ10.39(s,0.05H),9.25(d,J＝8.4Hz,1H),8.09(d,J＝8.2Hz,1H),7.98(dd,J＝7.0,1.2Hz,1H),7.92(d,J＝8.2Hz,1H),7.75–7.54(m,3H).13C NMR(100MHz,Chloroform-d)δ193.2(t,J＝26.7Hz),136.7,135.3,133.7,131.3(t,J＝3.5Hz),130.6,129.1,128.5,127.0,124.9.HRMS(ESI)Calculated forC11H8DO+([M+H]+):158.0711,found:158.0713。
Example 17
Firstly, weighing
(39.6mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then carefully add 2,4,6-Triisopropylthiophenol (0.03mmol,7.1mg) was then placed in a sealed tube under 5W blue LED lamp and reacted at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 20-10:1) to obtain product
28.2mg, 77% yield, D incorporation by1H NMR:94％.1H NMR(400MHz,Chloroform-d)δ9.98(s,0.06H),8.04(dd,J＝7.8,1.4Hz,1H),7.64(td,J＝7.5,1.4Hz,1H),7.55–7.42(m,5H),7.42–7.34(m,2H).13C NMR(100MHz,Chloroform-d)δ192.0(t,J＝27.1Hz),146.0,137.8,133.6,130.8,130.1,128.5,128.1,127.8,127.6.HRMS(ESI)Calculated for C13H10DO+([M+H]+):184.0867,found:184.0869。
Example 18
Firstly, weighing
(58.4mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) to obtain product
42.1mg, yield 76%, D incorporation by1H NMR:97％.1H NMR(400MHz,Chloroform-d)δ10.00(s,0.03H),7.90–7.84(m,1H),7.71(d,J＝8.3Hz,2H),7.63–7.55(m,1H),7.40(t,J＝8.0Hz,1H),7.34(d,J＝8.1Hz,2H),7.20(d,J＝8.2Hz,1H),2.46(s,3H).13C NMR(100MHz,Chloroform-d)δ186.9(t,J＝28.2Hz),151.2,146.3,135.3,131.3,130.2,129.2(t,J＝3.3Hz),128.6,128.5,127.6,123.7,21.8.HRMS(ESI)Calculated for C14H12DO4S+([M+H]+):278.0592,found:278.0593。
Example 19
Firstly, weighing
(35.6mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg, then sealed and placed under 5W blue LEDs lamp illumination at room temperature for 36h2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 30-10:1) to obtain product
24.8mg, yield 76%, D incorporation by1H NMR:95％.1H NMR(400MHz,Chloroform-d)δ9.97(s,0.05H),7.65–7.36(m,3H),7.24–7.19(m,1H),6.21–5.98(m,1H),5.44(dq,J＝17.3,1.6Hz,1H),5.32(dq,J＝10.5,1.5Hz,1H),4.61(dt,J＝5.3,1.5Hz,2H).13C NMR(100MHz,Chloroform-d)δ191.9(t,J＝26.5Hz),159.1,137.7(t,J＝3.4Hz),132.6,130.1,123.6,122.1,118.1,113.1,69.0.HRMS(ESI)Calculated for C10H10DO2 +([M+H]+):164.0816,found:164.0818。
Example 20
Firstly, weighing
(35.2mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 20-10:1) to obtain product
21.3mg, 66% yield, D incorporation by1H NMR:94％.1H NMR(400MHz,Chloroform-d)δ9.99(s,0.06H),7.56–7.44(m,3H),7.28–7.24(m,1H),4.76(s,2H),2.55(t,J＝2.4Hz,0.5H,50％D).13C NMR(100MHz,Chloroform-d)δ191.7(t,J＝26.7Hz),158.1,137.7(t,J＝3.6Hz),130.2,124.1,122.2,113.5,77.9,76.1,56.0.2H NMR(92MHz,Chloroform-d)δ10.03(s,1D),2.55(s,1D).HRMS(ESI)Calculated for C10H8DO2 +([M+H]+):162.0660,found:162.0664。
Example 21
Firstly, weighing
(35.2mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then carefully added2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was then placed in a tube under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing the solvent by rotary evaporation, loading the sample by a dry method, and performing column chromatography (300-400-mesh chromatography silica gel) (eluent: petroleum ether-ethyl acetate, volume ratio: 20-4:1) to obtain the product
19.2mg, yield 70%, D incorporation by1H NMR:95％.1H NMR(400MHz,Chloroform-d)δ10.00(s,0.05H),7.88(d,J＝8.2Hz,2H),7.53(d,J＝8.2Hz,2H),4.81(s,2H).13C NMR(100MHz,Chloroform-d)δ191.6(t,J＝26.4Hz),147.8,135.6(t,J＝3.6Hz),130.0,127.0,64.6.2H NMR(92MHz,Chloroform-d)δ10.06(s,1D).HRMS(ESI)Calculated for C8H8DO2 +([M+H]+):138.0660,found:138.0662。
Example 22
Firstly, weighing
(46.8mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio 10-5:1) to obtain product
26.3mg, 60% yield, D incorporation by 1H NMR:96％.1H NMR(400MHz,Chloroform-d)δ10.03(s,0.04H),8.30(s,1H),8.05(d,J＝6.2Hz,1H),7.94(d,J＝6.1Hz,1H),7.50(t,J＝7.5Hz,1H),3.79(s,4H),1.03(s,6H).13C NMR(100MHz,Chloroform-d)δ192.5(t,J＝26.5Hz),139.9,136.4,135.6(t,J＝3.1Hz),130.8,128.3,72.4,32.0,21.9.HRMS(ESI)Calculated for C12H15DBO3 +([M+H]+):220.1250,found:220.1253。
Example 23
Firstly, weighing
(49.6mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing the solvent by rotary evaporation, loading the sample by a dry method, and performing column chromatography (300-400-mesh chromatography silica gel) (eluent: petroleum ether-ethyl acetate, volume ratio: 15-5:1) to obtain the product
37.7mg, 81% yield, D incorporation by1H NMR:96％.1H NMR(400MHz,Chloroform-d)δ10.05(s,0.04H),7.96(d,J＝8.1Hz,2H),7.87(d,J＝8.2Hz,2H),1.37(s,12H).13C NMR(100MHz,Chloroform-d)δ192.5(t,J＝26.7Hz),138.03(t,J＝3.4Hz),135.2,128.7,84.3,24.9.HRMS(ESI)Calculated for C13H17DBO3 +([M+H]+):234.1406,found:234.1409。
Example 24
Firstly, weighing
(37.2mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 40-10:1) to obtain product
26.7mg, 78% yield, D incorporation by1H NMR:95％.1H NMR(400MHz,Chloroform-d)δ9.92(s,0.05H),7.44(s,1H),7.29(s,1H),7.16(s,1H),3.87(s,3H).13C NMR(100MHz,Chloroform-d)δ190.3(t,J＝27.2Hz),160.8,138.4(t,J＝3.6Hz),135.9,122.8,120.9,111.7,55.9.HRMS(ESI)Calculated forC8H7DClO2 +([M+H]+):172.0270,found:172.0272。
Example 25
Firstly, weighing
(33.2mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). Organic compoundsPhase channel anhydrous Na2SO4Drying, removing the solvent by rotary evaporation, loading the sample by a dry method, and performing column chromatography (300-400-mesh chromatography silica gel) (eluent: petroleum ether-ethyl acetate, volume ratio: 15-4:1) to obtain the product
15.1mg, 50% yield, D incorporation by1H NMR:94％.1H NMR(400MHz,Chloroform-d)δ11.59(br s,1H),10.01(s,0.06H),9.95(s,1H),8.15(d,J＝2.0Hz,1H),8.08(dd,J＝8.7,2.1Hz,1H),7.14(d,J＝8.7Hz,1H).13C NMR(100MHz,Chloroform-d)δ195.7(t,J＝27.5Hz),189.4,166.3,137.2,136.5,129.2,120.2(t,J＝3.1Hz),118.9.HRMS(ESI)Calculated for C8H6DO3 +([M+H]+):152.0452,found:152.0454。
Example 26
Firstly, weighing
(42.9mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 20-10:1) to obtain product
34.0mg, 85% yield, D incorporation by1H NMR:93％.1H NMR(400MHz,CDCl3)δ9.81(s,0.07H),7.32(d,J＝8.2Hz,1H),6.93–6.79(m,2H),6.20(br s,2H).13C NMR(100MHz,Chloroform-d)δ192.8(t,J＝26.5Hz),150.5,136.9,130.5,119.8,118.6,117.6(t,J＝3.2Hz).2H NMR(92MHz,Chloroform-d)δ9.85(s,1D).HRMS(ESI)Calculated for C7H6DBrNO+([M+H]+):200.9768,found:200.9769。
Example 27
Firstly, weighing
(34.6mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg, then sealed and placed under 5W blue LEDs lamp illumination at room temperature for 36h2SO4Drying, removing the solvent by rotary evaporation, loading the sample by a dry method, and performing column chromatography (300-400-mesh chromatography silica gel) (eluent: petroleum ether-ethyl acetate, volume ratio: 10-3:1) to obtain the product
14.2mg, 45% yield, D incorporation by1H NMR:95％.1H NMR(400MHz,CDCl3)δ10.21(s,0.05H),9.06(dd,J＝4.2,1.7Hz,1H),8.44–8.27(m,2H),8.22(d,J＝1.6Hz,2H),7.54(dd,J＝8.3,4.3Hz,1H).13C NMR(100MHz,Chloroform-d)δ191.1(t,J＝27.2Hz),153.1,150.9,137.5,134.2(t,J＝3.4Hz),133.6,130.8,127.7,126.8,122.2.HRMS(ESI)Calculated for C10H7DNO+([M+H]+):159.0663,found:159.0665。
Example 28
Firstly, weighing
(35.0mg, 0.2mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,1.0equiv.), and Ph3P (0.22mmol,57.6mg,1.1equiv.) was added to the reaction tube, the gas was evacuated three times through the vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.03mmol,7.1mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 20-10:1) to obtain product
29.4mg, yield 92%, D incorporation by1H NMR:96％.1H NMR(400MHz,Chloroform-d)δ9.89(s,0.04H),7.74(d,J＝8.1Hz,1H),7.53–7.33(m,2H),7.25(s,1H),7.22–7.15(m,1H),4.10(s,3H).13C NMR(100MHz,Chloroform-d)δ182.5(t,J＝27.0Hz),140.9,135.6(t,J＝4.3Hz),126.9,126.3,123.4,120.9,117.5,110.4,31.6.2H NMR(92MHz,Chloroform-d)δ9.91(s,1D).HRMS(ESI)Calculatedfor C10H9DNO+([M+H]+):161.0820,found:161.0822。
Example 29
Firstly, weighing
(29.8mg, 0.1mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,2.0equiv.), and Ph3P (0.11mmol,28.8mg,1.1equiv.) was added to the reaction tube, the tube was evacuated three times through a vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.02mmol,4.7mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, and rotary steamingRemoving the solvent, loading by a dry method, and performing column chromatography (300-400-mesh chromatography silica gel) (eluent: petroleum ether-ethyl acetate, volume ratio: 20-5:1) to obtain the product
26.0mg, yield 92%, Dincorporation by1H NMR:97％.1H NMR(400MHz,Chloroform-d)δ9.94(s,0.03H),7.64(d,J＝8.0Hz,1H),7.60(s,1H),7.45(d,J＝8.0Hz,1H),3.04–2.97(m,2H),2.54–2.41(m,2H),2.36(td,J＝10.8,3.9Hz,1H),2.22–2.02(m,3H),2.03–1.96(m,1H),1.76–1.40(m,6H),0.92(s,3H).13C NMR(100MHz,Chloroform-d)δ220.5,191.9(t,J＝26.3Hz),147.1,137.5,134.2(t,J＝3.1Hz),130.2,127.2,126.1,50.5,47.9,44.9,37.7,35.8,31.5,29.2,26.2,25.6,21.6,13.8.HRMS(ESI)Calculated for C19H22DO2 +([M+H]+):284.1755,found:284.1757。
Example 30
Firstly, weighing
(51.4mg, 0.1mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,2.0equiv.), and Ph3P (0.11mmol,28.8mg,1.1equiv.) was added to the reaction tube, the tube was evacuated three times through a vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.02mmol,4.7mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing the solvent by rotary evaporation, loading the sample by a dry method, and performing column chromatography (300-400-mesh chromatography silica gel) (eluent: petroleum ether-ethyl acetate, volume ratio: 4-1:1) to obtain the product
33.4mg, 67% yield, D incorporation by1H NMR:95％.1HNMR(400MHz,Chloroform-d)δ9.91(s,0.05H),7.99(d,J＝7.8Hz,1H),7.80–7.76(m,1H),7.63–7.56(m,1H),7.53–7.46(m,2H),7.41(s,1H),7.39–7.33(m,2H),7.32(s,1H),7.31–7.25(m,3H),7.14(d,J＝8.2Hz,2H),5.47(s,2H),3.81(s,3H),2.93(t,J＝7.8Hz,2H),2.77(s,3H),1.92–1.67(m,2H),1.05(t,J＝7.4Hz,3H).13C NMR(100MHz,Chloroform-d)δ191.8(t,J＝26.2Hz),156.4,154.6,145.0,143.2,142.8,137.5,136.7,136.0,135.1,133.7,132.0(t,J＝3.4Hz),130.7,129.5,128.0,127.8,126.2,124.1,123.9,122.6,122.4,119.5,109.6,108.9,46.8,31.8,29.8,21.9,16.9,14.1.HRMS(ESI)Calculated for C33H30DN4O+([M+H]+):500.2555,found:500.2557。
Example 31
Firstly, weighing
(41.2mg, 0.1mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,2.0equiv.), and Ph3P (0.11mmol,28.8mg,1.1equiv.) was added to the reaction tube, the tube was evacuated three times through a vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.02mmol,4.7mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing the solvent by rotary evaporation, loading the sample by a dry method, and performing column chromatography (300-400-mesh chromatography silica gel) (eluent: petroleum ether-ethyl acetate, volume ratio: 20-5:1) to obtain the product
29.0mg, 73% yield, D incorporation by1H NMR:96％.1H NMR(400MHz,Chloroform-d)δ10.15(s,0.04H),8.34(s,1H),8.09–8.01(m,2H),7.97(s,2H),7.84(dd,J＝8.4,1.7Hz,1H),7.61(d,J＝2.3Hz,1H),7.56(dd,J＝8.4,2.3Hz,1H),7.01(d,J＝8.4Hz,1H),3.91(s,3H),2.18(s,6H),2.11(s,3H),1.81(s,6H).13C NMR(100MHz,Chloroform-d)δ192.1(t,J＝27.0Hz),159.1,142.3,139.1,137.0,134.4,133.7(t,J＝3.1Hz),132.3,131.4,129.9,129.2,126.9,126.0,125.8,125.0,123.2,112.1,55.2,40.6,37.2,37.1,29.1.HRMS(ESI)Calculated for C28H28DO2 +([M+H]+):398.2225,found:398.2227。
Example 32
Firstly, weighing
(46.4mg, 0.1mmol), photocatalyst Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(34.8mg,2.0equiv.), and Ph3P (0.11mmol,28.8mg,1.1equiv.) was added to the reaction tube, the tube was evacuated three times through a vacuum line, and DCM/D was added under an argon atmosphere2O (2.0mL,1:1v/v), then 2,4, 6-triisopropylthiophenol (0.02mmol,4.7mg) was added carefully, and the tube was sealed and placed under 5W blue LEDs for reaction at room temperature for 36 h. The reaction was complete and the mixture was quenched with water and extracted with DCM (3 × 10 mL). The organic phase is passed through anhydrous Na2SO4Drying, removing solvent by rotary evaporation, loading by dry method, and performing column chromatography (300-400 mesh silica gel chromatography) (eluent: petroleum ether-ethyl acetate, volume ratio: 30-10:1) to obtain product
28.7mg, yield 64%, D incorporation by1H NMR:94％.1H NMR(400MHz,Chloroform-d)δ10.07(s,0.06H),8.52(s,1H),8.29(d,J＝10.7Hz,1H),8.07(d,J＝10.5Hz,1H),7.62(t,J＝7.7Hz,1H),5.42(d,J＝4.7,1H),4.94-4.83(m,1H),2.55–2.40(m,3H),2.20(d,J＝10.8Hz,1H),2.12(s,3H),2.05–1.99(m,3H),1.93(dt,J＝13.3,3.4Hz,1H),1.77–1.43(m,9H),1.27–1.18(m,3H),1.07(s,3H),0.63(s,3H).13C NMR(100MHz,Chloroform-d)δ209.6,191.1(t,J＝27.8Hz),164.9,139.4,136.4(t,J＝3.5Hz),135.2,133.1,131.9,131.1,129.2,122.7,75.1,63.7,56.8,49.9,44.0,38.8,38.1,37.0,36.7,31.8,31.8,31.6,27.8,24.5,22.8,21.1,19.4,13.2.2H NMR(92MHz,Chloroform-d)δ10.13(s,1D).HRMS(ESI)Calculated for C29H36DO4 +([M+H]+):450.2749,found:450.2752。
Example of deuterated fatty aldehyde preparation:
example 33
Firstly, weighing
(15.1mg, 0.1mmol), photocatalyst Ir [ dF (Me) ppy]2(dtbbpy)PF6(2.5mg,0.0025mmol) was added to the reaction tube, the tube was evacuated three times through a vacuum line, toluene (5.0mL) was added under an argon atmosphere, then 2,4, 6-triisopropylthiophenol (0.04mmol,9.4 mg), diphenylethoxyphosphine (0.12mmol,27.6mg), 2, 6-lutidine (0.12mmol,12.8mg) were carefully added and the tube was sealed and placed under a 45W blue LED lamp for reaction at room temperature for 36 h. After the reaction is finished, the solvent is removed under reduced pressure, the dry method is used for sample loading, and the product is obtained by column chromatography (300-400 mesh chromatography silica gel) (eluent: petroleum ether-ethyl acetate, volume ratio: 100-50:1)
7.6mg, 56% yield, D incorporation by1H NMR:63％.1H NMR(400MHz,Chloroform-d)δ9.82(s,0.37H),7.29(t,J＝7.3Hz,2H),7.23–7.16(m,3H),2.96(t,J＝7.5Hz,2H),2.78(t,J＝7.5Hz,2H).13C NMR(100MHz,Chloroform-d)δ201.1(t,J＝26.2Hz),140.3,128.6,128.3,126.3,45.3,28.1.HRMS(ESI)Calculated for C9H10DO+([M+H]+):136.0867,found:136.0870。
Example 34
Firstly, weighing
(19.7mg, 0.1mmol), photocatalyst Ir [ dF (Me) ppy]2(dtbbpy)PF6(2.5mg,0.0025mmol) was added to the reaction tube, the tube was evacuated three times through a vacuum line, toluene (5.0mL) was added under an argon atmosphere, then 2,4, 6-triisopropylthiophenol (0.04mmol,9.4 mg), diphenylethoxyphosphine (0.12mmol,27.6mg), 2, 6-lutidine (0.12mmol,12.8mg) were carefully added and the tube was sealed and placed under a 45W blue LED lamp for reaction at room temperature for 36 h. Inverse directionAfter the reaction is finished, the solvent is removed under reduced pressure, the dry method is used for sample loading, and the product is obtained by column chromatography (300-400-mesh chromatography silica gel) (eluent: petroleum ether-ethyl acetate, volume ratio: 100-50:1)
7.4mg, 41% yield, dr 5:1, D incorporation by1H NMR:58％.1HNMR(400MHz,CDCl3)δ9.34(d,J＝4.5Hz,0.42H),7.26(d,J＝8.4,2H),7.04(d,J＝8.4Hz,2H),2.63–2.57(m,1H),2.18–2.12(m,1H),1.77–1.68(m,1H),1.54–1.44(m,1H).13C NMR(100MHz,Chloroform-d)δ199.1(t,J＝23.2Hz),137.5,132.6,128.7,127.7,33.7,26.0,16.5.HRMS(ESI)Calculated for C10H9DClO+([M+H]+):182.0477,found:182.0479。
Example 35
Firstly, weighing
(16.3mg, 0.1mmol), photocatalyst Ir [ dF (Me) ppy]2(dtbbpy)PF6(2.5mg,0.0025mmol) was added to the reaction tube, the tube was evacuated three times through a vacuum line, toluene (5.0mL) was added under an argon atmosphere, then 2,4, 6-triisopropylthiophenol (0.04mmol,9.4 mg), diphenylethoxyphosphine (0.12mmol,27.6mg), 2, 6-lutidine (0.12mmol,12.8mg) were carefully added and the tube was sealed and placed under a 45W blue LED lamp for reaction at room temperature for 36 h. After the reaction is finished, the solvent is removed under reduced pressure, the dry method is used for sample loading, and the product is obtained by column chromatography (300-400 mesh chromatography silica gel) (eluent: petroleum ether-ethyl acetate, volume ratio: 100-50:1)
8.8mg, yield 60%, D incorporation by1H NMR:75％.1H NMR(400MHz,Chloroform-d)δ9.77(d,J＝1.3Hz,0.24H),7.29–7.20(m,2H),7.17–7.11(m,2H),3.37–3.24(m,3H),3.22–3.12(m,2H).13C NMR(100MHz,Chloroform-d)δ202.6(t,J＝23.2Hz),141.1,126.8,124.6,50.7,32.9.HRMS(ESI)Calculated for C10H10DO+([M+H]+):148.0867,found:148.0868。
Example 36
Firstly, weighing
(35.2mg, 0.1mmol), photocatalyst Ir [ dF (Me) ppy]2(dtbbpy)PF6(2.5mg,0.0025mmol) was added to the reaction tube, the tube was evacuated three times through a vacuum line, toluene (5.0mL) was added under an argon atmosphere, then 2,4, 6-triisopropylthiophenol (0.04mmol,9.4 mg), diphenylethoxyphosphine (0.12mmol,27.6mg), 2, 6-lutidine (0.12mmol,12.8mg) were carefully added and the tube was sealed and placed under a 45W blue LED lamp for reaction at room temperature for 36 h. After the reaction is finished, the solvent is removed under reduced pressure, the dry method is used for sample loading, and the product is obtained by column chromatography (300-400 mesh chromatography silica gel) (eluent: petroleum ether-ethyl acetate, volume ratio: 10-2:1)
19.2mg, 57% yield, D incorporation by1H NMR:72％.1H NMR(400MHz,CDCl3)δ9.64(s,0.28H),7.76(d,J＝7.5Hz,2H),7.57(d,J＝7.5Hz,2H),7.40(t,J＝7.4Hz,2H),7.31(t,J＝7.9Hz,2H),4.45(s,2H),4.24(t,J＝6.6Hz,1H),4.02-3.91(m,2H),2.99(t,J＝12.1Hz,2H),2.66–2.26(m,1H),1.87(s,2H),1.50(s,2H).13C NMR(100MHz,Chloroform-d)δ202.3(t,J＝26.2Hz),155.1,144.0,141.4,127.7,127.1,124.9,120.0,67.2,47.7,47.4,43.0,25.0.HRMS(ESI)Calculated for C21H21DNO3 +([M+H]+):337.1657,found:337.1658。
Claims (10)
1. A method for preparing deuterated aldehyde from aromatic carboxylic acid under blue light irradiation by using an iridium complex as a catalyst is characterized by comprising the following steps: it uses aromatic carboxylic acid as raw material, triphenylphosphine as deoxidant, under the irradiation of blue light lamp, in the solution of dichloromethane and heavy water, in which the volume ratio of dichloromethane and heavy water is 1:1, quickly stirring them, under the condition of argon atmosphere and using dipotassium hydrogen phosphate as alkali, using [ Ir (dF (CF) as deoxidant3)ppy)2(dtbbpy)]PF6The 2,4, 6-triisopropylthiophenol is used as a photocatalyst and is used as an organic small molecule catalystAnd (4) oxidizing the aldehyde to obtain the deuterated aromatic aldehyde compound.
2. The method of claim 1, wherein: the Ar group in the aromatic carboxylic acid is various substituted aryl or heteroaryl.
3. The method of claim 1, wherein: the mass ratio of the aromatic carboxylic acid to the triphenylphosphine is 1: 1-2.
4. The method of claim 1, wherein: the mass ratio of the dipotassium hydrogen phosphate to the aromatic carboxylic acid is 1: 1-2.
5. The method of claim 1, wherein: the photocatalyst [ Ir (dF (CF) ]3)ppy)2(dtbbpy)]PF6In a molar amount of 1% of the moles of aromatic carboxylic acid; the amount of the 2,4, 6-triisopropylthiophenol catalyst used is 15 mol% of the moles of the aromatic carboxylic acid.
6. A method for preparing deuterated aldehyde from aliphatic carboxylic acid under the irradiation of blue light by taking an iridium complex as a catalyst is characterized by comprising the following steps: it uses deuterated aliphatic carboxylic acid as raw material, uses diphenyl ethoxy phosphine as deoxidant and uses [ Ir (dF (Me) ppy)2(dtbbpy)]PF6The method is characterized in that 2,4, 6-triisopropylthiophenol is a small organic molecular catalyst, and a deuterated aliphatic aldehyde compound is obtained under the irradiation of a blue light lamp and in the presence of 2, 6-dimethylpyridine in a toluene solution and an argon atmosphere.
7. The method of claim 6, wherein: the fatty carboxylic acid is fatty carboxylic acid with various alkyl groups.
8. The method of claim 6, wherein: the mass ratio of the fatty carboxylic acid to the diphenyl ethoxy phosphine is 1: 1-2.
9. The method of claim 6, wherein: the mass ratio of the 2, 6-lutidine to the fatty carboxylic acid is 1: 1-2.
10. The method of claim 6, wherein: the photocatalyst [ Ir (dF (Me) ppy)2(dtbbpy)]PF6The amount used is 2.5% of the molar amount of the aliphatic carboxylic acid; the amount of the 2,4, 6-triisopropylthiophenol catalyst used is 40 mol% of the moles of the aliphatic carboxylic acid.
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| CN107827687A (en) * | 2017-07-24 | 2018-03-23 | 山东辉璟生物医药科技有限公司 | A kind of synthetic method of cold labeling chloramphenicol |
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Non-Patent Citations (2)
| Title |
|---|
| A general deoxygenation approach for synthesis of ketones from aromatic carboxylic acids and alkenes;Muliang Zhang等;《NATURE COMMUNICATIONS》;20180829;第9卷(第1期);1-10 * |
| On the Enthalpy of Formation of Hydroxyl Radical and Gas-Phase Bond Dissociation Energies of Water and Hydroxyl;Branko Ruscic等;《J. Phys. Chem. A》;20020227;第106卷;2727-2747 * |
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