CN113968883A - Optical chromone derivative and preparation method thereof - Google Patents
Optical chromone derivative and preparation method thereof Download PDFInfo
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- CN113968883A CN113968883A CN202010718654.3A CN202010718654A CN113968883A CN 113968883 A CN113968883 A CN 113968883A CN 202010718654 A CN202010718654 A CN 202010718654A CN 113968883 A CN113968883 A CN 113968883A
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- C—CHEMISTRY; METALLURGY
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- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
- C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom
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Abstract
The invention discloses an optical chromone derivative, which is characterized in that (S) -2- (diphenylphosphinoyl) chromium-4-ketone and borane are subjected to reduction reaction to obtain a first intermediate, the first intermediate is subjected to Mitsunobu reaction to obtain a second intermediate, the second intermediate is subjected to substituent removal under an alkaline condition to obtain a third intermediate, and the third intermediate and imidazole-4-methyl formate are subjected to Mitsunobu reaction again to obtain a target product, namely a novel optical chromone derivative, wherein the structure of the novel optical chromone derivative is shown in the following formula (I). The invention creatively researches a preparation method of a novel optical chromone derivative, adopts Mitsunobu reaction to generate configuration inversion, expands the diversity of a chromone compound chiral framework and effectively expands the synthesis application of an organic phosphine compound.
Description
Technical Field
The invention belongs to the technical field of chemical preparation, and particularly relates to an optical chromone derivative and a preparation method thereof.
Background
As the research of people on compounds shows, organic compounds with chirality have good physiological activity and pharmacological activity, and efficient and accurate chiral synthesis has very important value in the fields of drug research and development, material science, pesticide development and the like, so that the synthesis and research of chiral compounds become research hotspots and difficulties in the fields of drugs, biology and the like. Meanwhile, the organic phosphine compound with high optical activity is very important in the aspects of synthesis, research and application. In 2013, frank glory topic group (angelw. chem. int.ed.,2013,52, 8454-; subsequently in 2018, a topic group (chem. Commun.,2018,54, 13571-13574) reported that such chromone structures synthesized a class of nitrogen-containing compounds through reactions, which could be used as pesticides. Therefore, based on the original research, the novel optical chromone derivative is synthesized by adopting an efficient method.
The novel optical chromone derivative contains heteroatoms, has good biological activity and can be used in the fields of pesticide development and the like; meanwhile, the chromone derivative contains a phosphine element, can be used for synthesizing a chiral phosphine nitride ligand through subsequent conversion, is used for asymmetric catalytic reaction and synthesis, and has great value for solving the limitation of asymmetric catalytic reaction.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide an optical chromone derivative with higher yield and purity and a preparation method thereof aiming at the defects of the prior art.
The technical scheme is as follows: the optical chromone derivative is characterized by being shown as a formula (I) and a formula (VI):
wherein: r1Is 6-F, 6-Cl, 6-Br, 6-OMe, 6-CO2Me、6-NO25-Me, 6-Me, 7-Me or 8-Me;
R2me or Et;
ar is C6H5-、2-Me-C6H4-、3-Me-C6H4-、4-Me-C6H4-、4-F-C6H4-or 2-naphthyl-.
The invention also provides a preparation method of the optical chromone derivative, which comprises the following steps:
(1) adding a mixture of 1: reacting 1-2 parts of (S) -2- (diphenylphosphine acyl) chromium-4-ketone (V) and borane tetrahydrofuran complex for 2-4 hours at the temperature of-2 ℃, adding a quenching agent methanol after the reaction is finished, extracting and drying, evaporating a solvent, and performing column chromatography separation by using petroleum ether/ethyl acetate to obtain a first intermediate as shown in a formula (IV);
(2) adding a first nucleophilic reagent, a first phosphine ligand, a first azo reagent and a first solvent into the first intermediate, reacting at room temperature for 3-5 hours, evaporating the solvent after the reaction is finished, and performing column chromatography separation by using petroleum ether/ethyl acetate to obtain a second intermediate, wherein the second intermediate is shown in a formula (III);
(3) adding alkali and a second solvent into the second intermediate, reacting for 1-2 hours at room temperature, extracting after the reaction is finished, drying, evaporating the solvent, and performing column chromatography separation by using petroleum ether/ethyl acetate to obtain a third intermediate shown as a formula (II);
(4) adding a second nucleophilic reagent, a second phosphine ligand, a second azodicarboxylate and a third solvent into the third intermediate, heating to room temperature at-35-25 ℃ for reaction for 12 hours, evaporating the solvent after the reaction is finished, and performing column chromatography separation by using petroleum ether/ethyl acetate to obtain an R-type optical chromone derivative shown in formula (I);
(5) adding a third nucleophilic reagent, a third phosphine ligand, a third azodicarboxylate and a fourth solvent into the first intermediate, heating to room temperature at-35-25 ℃ for reaction for 12 hours, evaporating the solvent after the reaction is finished, and performing column chromatography separation by using petroleum ether/ethyl acetate to obtain an S-type optical chromone derivative shown in a formula (VI);
the specific reaction process is as follows:
further, as a preferred embodiment, in the step (2), the first nucleophile is p-nitrobenzoic acid, the first phosphine ligand is triphenylphosphine, the first azo reagent is diisopropyl azodicarboxylate, and the first solvent is tetrahydrofuran.
Further, as a preferred example, the base in the step (3) is potassium carbonate, and the second solvent is methanol.
Further, as a preferred embodiment, in the step (4), the second nucleophile is imidazole-4-methyl formate, the second phosphine ligand is triphenylphosphine, the second azo reagent is diisopropyl azodicarboxylate, and the third solvent is tetrahydrofuran.
Further, as a preferred embodiment, in the step (5), the third nucleophile is imidazole-4-methyl formate, the third phosphine ligand is triphenylphosphine, the third azo reagent is diisopropyl azodicarboxylate, and the fourth solvent is tetrahydrofuran.
Has the advantages that: the invention pioneers a preparation method of a novel optical chromone derivative, and researches conditions such as raw material characteristics, product structure and the like by an inventor, adopts Mitsunobu reaction to reverse the configuration to obtain two intermediates with opposite configurations, and then selects a better route to synthesize the novel chromone derivative, so that the reaction can be smoothly carried out, and the novel chromone derivative has higher yield and purity; on the other hand, the application of the organic phosphine compound in synthesis is expanded, the diversity of the organic phosphine compound is enriched, and the method has guiding significance for the research and development of the organic nitrogen phosphine compound in the future.
Drawings
FIG. 1 is a drawing of the product of example 11H NMR spectrum;
FIG. 2 is a drawing of the product of example 113C NMR spectrum;
FIG. 3 is a drawing of the product of example 131A P NMR spectrum;
FIG. 4 is a graph of the product of example 21H NMR spectrum;
FIG. 5 is a graph of the product of example 213C NMR spectrum;
FIG. 6 is a graph of the product of example 231A P NMR spectrum;
FIG. 7 is a graph of the product of example 31H NMR spectrum;
FIG. 8 is a graph of the product of example 313C NMR spectrum;
FIG. 9 is a graph of a product obtained in example 3Of an object31A P NMR spectrum;
FIG. 10 is the product of example 41H NMR spectrum;
FIG. 11 is a graph of the product of example 413C NMR spectrum;
FIG. 12 is a graph of the product of example 431A P NMR spectrum;
FIG. 13 is a photograph of the product of example 51H NMR spectrum;
FIG. 14 is a photograph of the product of example 513C NMR spectrum;
FIG. 15 is a photograph of the product of example 531P NMR spectrum.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the embodiments. The reaction drugs used in the examples are all conventionally commercially available.
Example 1: preparation of the first intermediate
At room temperature and N2Under protection, 1.74g of (S) -2- (diphenylphosphine acyl) chromium-4-ketone is added into a dry reaction bottle, after 25ml of tetrahydrofuran solution is added, the reaction system is cooled to 0 ℃, kept at the temperature for 5 minutes, 10ml of borane tetrahydrofuran complex with the purity of 1M in tetrahydrofuran is slowly dripped, and the reaction is carried out for 2 hours at the temperature of 0 ℃ after the dripping is finished; after the reaction is finished, 5mL of methanol solution is slowly added at 0 ℃ for quenching, then 50mL of water is added, standing is carried out for layering, an organic phase is separated by a separating funnel, an aqueous phase is extracted by 20mL of ethyl acetate for three times, the combined organic phase is dried by anhydrous sodium sulfate, and then filtration and decompression are carried out to remove the solvent, so as to obtain a crude product. Purifying the crude product by column chromatography with n-hexane and ethyl acetate as eluent at a ratio of 3:1 to obtain 1.72g of a compound, namely a first intermediate, with a yield of 98% and a dr value greater than 20:1, determined by nuclear magnetic resonance spectrogram analysis.
The structural characterization data for the product obtained in example 1 are shown below:
1H NMR(500MHz,CDCl3):δ7.87(dt,J＝11.3,6.9Hz,4H),7.61–7.47(m,5H),7.45(td,J＝7.7,3.0Hz,2H),7.12(td,J＝7.8,1.7Hz,1H),6.95(t,J＝7.4Hz,1H),6.73(d,J＝8.2Hz,1H),5.09(dd,J＝8.2,4.2Hz,1H),4.85(t,J＝6.3Hz,1H),2.77–2.69(m,1H),2.09(dq,J＝14.0,6.9Hz,1H).
13C NMR(126MHz,CDCl3):δ152.83(d,J＝5.9Hz),132.44(d,J＝2.7Hz),132.34(d,J＝2.8Hz),132.03(d,J＝9.1Hz),131.47(d,J＝9.2Hz),130.35,129.70,128.91,128.84,128.79(d,J＝9.0Hz),128.52(d,J＝11.9Hz),128.24,125.64,121.56,116.24,72.28(d,J＝86.3Hz),62.66(d,J＝10.2Hz),30.86.
31P NMR(203MHz,CDCl3):δ31.34,29.82.
the successful synthesis of the first intermediate is proved by the nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the phosphine spectrum of the product.
The specific optical rotation of the compound of formula (IV) [ alpha ]]D 25＝-70°(c＝0.10,MeOH).
HRMS:calculated for C21H19O3P(M+H)+:351.1145,found:351.1149.
The above proves that the first intermediate is successfully synthesized, and the yield and the purity are higher.
Example 2: preparation of the second intermediate
At 0 ℃ and N2Under the protection of (1.72 g), 1.72g of the first intermediate, 983mg of p-nitrobenzoic acid and 1.55g of triphenylphosphine were added to 44ml of a tetrahydrofuran solution and stirred at 0 ℃ for 5 minutes; simultaneously dissolving 1.3g of diisopropyl azodicarboxylate into 15ml of tetrahydrofuran solution, then dropwise adding the solution into the reaction system, and moving the reaction system to room temperature for reaction for 2 hours; after the reaction is finished, the solvent is removed under reduced pressure to obtain a crude product. Purifying the crude product by column chromatography with n-hexane and ethyl acetate as eluent in a ratio of 3:1 to obtain 2.29g of a compound, namely a second intermediate, with a yield of 99%; dr value greater than 20:1, as determined by nuclear magnetic resonance spectroscopy analysis.
The structural characterization data for the product obtained in example 2 are shown below:
1H NMR(500MHz,CDCl3):δ8.27–8.23(m,2H),8.20–8.15(m,2H),8.07–7.92(m,4H),7.64–7.49(m,6H),7.40(dd,J＝7.7,1.7Hz,1H),7.28(ddd,J＝8.8,7.3,1.7Hz,1H),7.00–6.93(m,2H),6.25(d,J＝2.8Hz,1H),5.23(ddd,J＝13.4,5.0,2.1Hz,1H),2.78(dd,J＝14.9,2.2Hz,1H),2.18–2.07(m,1H).
13C NMR(126MHz,CDCl3):δ163.86,154.30(d,J＝9.6Hz),150.67,135.33,132.58(d,J＝2.4Hz),132.44(d,J＝8.5Hz),131.62,131.55(d,J＝2.5Hz),131.23,131.00,130.95,130.56,129.76,128.70(dd,J＝28.5,11.7Hz),127.11,123.55,121.79,119.22,117.27,69.97(d,J＝92.9Hz),65.81(d,J＝10.8Hz),27.51.
31P NMR(203MHz,CDCl3):δ31.34,29.82.
the successful synthesis of the second intermediate is proved by the nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the phosphine spectrum of the product
The specific optical rotation of the compound of formula (III) [ alpha ]]D 25＝-103°(c＝0.10,MeOH).
HRMS:calculated for C28H22NO6P(M+Na)+:522.1077,found:522.1082.
The second intermediate is successfully synthesized, and the yield and the purity are higher.
Example 3: preparation of third intermediate
670mg of the second intermediate was dissolved in 54ml of a methanol solution at room temperature, followed by addition of 448mg of solid potassium carbonate and reaction for 1 hour; after the reaction is finished, filtering by using kieselguhr, and removing the solvent by using organic phase under reduced pressure to obtain a crude product. Purifying the crude product by column chromatography with n-hexane and ethyl acetate as eluent at a ratio of 1:1 to obtain 410mg of a second intermediate with a yield of 88%; dr value greater than 20:1, as determined by nuclear magnetic resonance spectroscopy analysis.
The structural characterization data for the product obtained in example 3 are shown below:
1H NMR(500MHz,CDCl3):δ7.95–7.85(m,4H),7.54(tdd,J＝7.3,3.2,1.5Hz,2H),7.48–7.41(m,4H),7.29(dd,J＝7.7,1.7Hz,1H),7.16(ddd,J＝8.6,7.3,1.7Hz,1H),6.90(td,J＝7.4,1.2Hz,1H),6.81(dd,J＝8.3,1.1Hz,1H),5.36(ddd,J＝13.1,4.1,2.0Hz,1H),4.82(q,J＝2.8Hz,1H),2.57(dq,J＝14.1,2.4Hz,1H),1.90(tdd,J＝13.7,7.7,3.2Hz,1H).
13C NMR(126MHz,CDCl3):δ153.58(d,J＝10.2Hz),132.33(d,J＝9.1Hz),132.26(d,J＝2.7Hz),131.56(d,J＝9.3Hz),131.16,130.82,130.36,129.47,128.87,128.51(dd,J＝28.6,11.9Hz),128.08,123.87,121.25,116.86,68.95(d,J＝94.5Hz),61.81(d,J＝11.3Hz),29.85.
31P NMR(203MHz,CDCl3):δ30.17.
the successful synthesis of the third intermediate is proved by the nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the phosphine spectrum of the product.
The specific optical rotation of the compound of formula (II) < alpha > [ alpha ]]D 25＝-46°(c＝0.10,MeOH).
HRMS:calculated for C21H19O3P(M+H)+:351.1145,found:351.1241.
The third intermediate is successfully synthesized, and the yield and the purity are higher.
Example 4: preparation of novel optical chromone derivatives
In N2Under the conditions of (1), 175mg of the third intermediate, 76mg of imidazole-4-carboxylic acid methyl ester and 158mg of triphenylphosphine were sequentially added to a dry reaction tube, and 4.5ml of a tetrahydrofuran solution was added thereto and stirred at a temperature of-30 ℃; meanwhile, 132mg of diisopropyl azodicarboxylate is dissolved in 1.5ml of tetrahydrofuran solution, and then the solution is dropwise added into the reaction system and is moved to room temperature for reaction for 12 hours; after the reaction is finished, the solvent is removed under reduced pressure to obtain a crude product. Purifying the crude product by column chromatography with n-hexane and ethyl acetate as eluent in a ratio of 1:1 to obtain 126mg of a compound, namely a target product, a novel optical chromone derivative with a yield of 55%; dr value greater than 20:1, as determined by nuclear magnetic resonance spectroscopy analysis.
The structural characterization data for the product obtained in example 4 are as follows:
1H NMR(500MHz,CDCl3):δ7.93(q,J＝11.1,10.4Hz,4H),7.79(s,1H),7.59(q,J＝7.0Hz,2H),7.56–7.48(m,4H),7.47(s,1H),7.20(t,J＝7.8Hz,1H),6.89(dd,J＝13.3,7.7Hz,2H),6.80–6.75(m,1H),6.73(d,J＝8.4Hz,1H),5.13(dd,J＝12.3,5.1Hz,1H),3.88(s,3H),2.99(dd,J＝13.5,6.2Hz,1H),2.08(qd,J＝12.5,7.0Hz,1H).
13C NMR(126MHz,CDCl3):δ160.45,154.33(d,J＝10.6Hz),139.82,136.28,132.62(dd,J＝16.1,2.8Hz),132.25(d,J＝9.0Hz),131.45(d,J＝9.3Hz),130.82,130.02,129.80,128.73(dd,J＝14.1,11.8Hz),128.38,127.58,127.41,123.15,122.28,121.19,117.49,73.57(d,J＝90.8Hz),51.90,50.92(d,J＝15.2Hz),30.59.
31P NMR(203MHz,CDCl3):δ28.13,27.44.
the successful synthesis of the novel optical chromone derivative is proved by the nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the phosphine spectrum of the product.
The specific optical rotation of the compound of formula (I) [ alpha ]]D 25＝-51°(c＝0.10,MeOH).
HRMS:calculated for C26H23N2O4P(M+H)+:459.1474,found:459.1475.
The results prove that the novel optical chromone derivative is successfully synthesized, and the yield and the purity are higher.
Example 5: preparation of novel optical chromone derivatives
In N2Under the conditions of (1), 175mg of the first intermediate, 76mg of imidazole-4-carboxylic acid methyl ester and 158mg of triphenylphosphine were sequentially added to a dry reaction tube, and 4.5ml of a tetrahydrofuran solution was added thereto and stirred at a temperature of-30 ℃; meanwhile, 132mg of diisopropyl azodicarboxylate is dissolved in 1.5ml of tetrahydrofuran solution, and then the solution is dropwise added into the reaction system and is moved to room temperature for reaction for 12 hours; after the reaction is finished, the solvent is removed under reduced pressure to obtain a crude product. Purifying the crude product by column chromatography with n-hexane and ethyl acetate as eluent in a ratio of 1:1 to obtain 121mg of a compound, namely a target product, the R-type optical chromone derivative with a yield of 53%; dr value greater than 20:1, as determined by nuclear magnetic resonance spectroscopy analysis.
The structural characterization data for the product obtained in example 5 are shown below:
1H NMR(600MHz,CDCl3):δ7.90(ddd,J＝19.3,11.5,8.2Hz,4H),7.82(s,1H),7.62–7.53(m,2H),7.50(dtd,J＝18.5,7.7,3.0Hz,4H),7.31(t,J＝7.0Hz,1H),7.23(s,1H),7.09(d,J＝6.5Hz,1H),6.98(t,J＝7.5Hz,2H),6.22–6.15(m,1H),4.68(ddd,J＝13.4,5.7,2.1Hz,1H),3.88(s,3H),2.70(dd,J＝15.1,2.2Hz,1H),2.31–2.20(m,1H).
13C NMR(151MHz,CDCl3):δ160.53,154.33(d,J＝9.3Hz),141.52,138.20,132.51(t,J＝3.1Hz),132.39(d,J＝8.7Hz),131.49(d,J＝9.3Hz),131.15,130.88,130.21,128.64(dd,J＝29.9,11.9Hz),128.39,127.73,122.61,122.35,117.67,117.04,68.74(d,J＝91.9Hz),50.11(d,J＝11.6Hz),28.82.
31P NMR(203MHz,CDCl3):δ29.34,28.04.
the successful synthesis of the novel optical chromone derivative is proved by the nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the phosphine spectrum of the product.
The specific optical rotation of the compound of formula (VI) [ alpha ]]D 25＝-39°(c＝0.10,MeOH).
HRMS:calculated for C26H23N2O4P(M+H)+:459.1474,found:459.1475.
The S-type optical chromone derivative is successfully synthesized, and the yield and the purity are higher.
The invention pioneers a preparation method of a novel optical chromone derivative, and through the research of conditions such as raw material characteristics, product structure and the like by the inventor, a better route is selected to synthesize the novel chromone derivative, so that the smooth proceeding of the reaction process is ensured, and the derivative has higher yield and purity; on the other hand, the application of the organic phosphine compound in synthesis is expanded, the diversity of the organic phosphine compound is enriched, and the method has guiding significance for the research and development of the organic nitrogen phosphine compound in the future.
As noted above, while the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limited thereto. Various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. An optical chromone derivative, characterized by the formula (I) and the formula (VI):
wherein: r1Is 6-F, 6-Cl, 6-Br, 6-OMe, 6-CO2Me、6-NO25-Me, 6-Me, 7-Me or 8-Me;
R2me or Et;
ar is C6H5-、2-Me-C6H4-、3-Me-C6H4-、4-Me-C6H4-、4-F-C6H4-or 2-naphthyl-.
2. A method for preparing the optical chromone derivative of claim 1, which comprises the following steps:
(1) adding a mixture of 1: reacting 1-2 parts of (S) -2- (diphenylphosphine acyl) chromium-4-ketone (V) and borane tetrahydrofuran complex for 2-4 hours at the temperature of-2 ℃, adding a quenching agent methanol after the reaction is finished, extracting and drying, evaporating a solvent, and performing column chromatography separation by using petroleum ether/ethyl acetate to obtain a first intermediate as shown in a formula (IV);
(2) adding a first nucleophilic reagent, a first phosphine ligand, a first azo reagent and a first solvent into the first intermediate, reacting at room temperature for 3-5 hours, evaporating the solvent after the reaction is finished, and performing column chromatography separation by using petroleum ether/ethyl acetate to obtain a second intermediate, wherein the second intermediate is shown in a formula (III);
(3) adding alkali and a second solvent into the second intermediate, reacting for 1-2 hours at room temperature, extracting after the reaction is finished, drying, evaporating the solvent, and performing column chromatography separation by using petroleum ether/ethyl acetate to obtain a third intermediate shown as a formula (II);
(4) adding a second nucleophilic reagent, a second phosphine ligand, a second azodicarboxylate and a third solvent into the third intermediate, heating to room temperature at-35-25 ℃ for reaction for 12 hours, evaporating the solvent after the reaction is finished, and performing column chromatography separation by using petroleum ether/ethyl acetate to obtain an R-type optical chromone derivative shown in formula (I);
(5) adding a third nucleophilic reagent, a third phosphine ligand, a third azodicarboxylate and a fourth solvent into the first intermediate, heating to room temperature at-35-25 ℃ for reaction for 12 hours, evaporating the solvent after the reaction is finished, and performing column chromatography separation by using petroleum ether/ethyl acetate to obtain an S-type optical chromone derivative shown in a formula (VI);
the specific reaction process is as follows:
3. the method for preparing an optical chromone derivative according to claim 2, wherein: in the step (2), the first nucleophilic reagent is p-nitrobenzoic acid, the first phosphine ligand is triphenylphosphine, the first azo reagent is diisopropyl azodicarboxylate, and the first solvent is tetrahydrofuran.
4. The method for preparing an optical chromone derivative according to claim 2, wherein: in the step (3), the alkali is potassium carbonate, and the second solvent is methanol.
5. The method for preparing an optical chromone derivative according to claim 2, wherein: in the step (4), the second nucleophilic reagent is imidazole-4-methyl formate, the second phosphine ligand is triphenylphosphine, the second azo reagent is diisopropyl azodicarboxylate, and the third solvent is tetrahydrofuran.
6. The method for preparing an optical chromone derivative according to claim 2, wherein: in the step (5), the third nucleophilic reagent is imidazole-4-methyl formate, the third phosphine ligand is triphenylphosphine, the third azo reagent is diisopropyl azodicarboxylate, and the fourth solvent is tetrahydrofuran.
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| RYOTA ISSHIKI ET AL: "Decarbonylative C-P Bond Formation Using Aromatic Esters and Organophosphorus Compounds", 《ORG. LETT.》 * |
| YUJIE MA ET AL: "Synthesis of chiral chromanols via a RuPHOX–Ru catalyzed asymmetric hydrogenation of chromones", 《CHEM. COMMUN.》 * |
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