CN115197271B - Selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol (amine) and synthetic method thereof - Google Patents
Selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol (amine) and synthetic method thereof Download PDFInfo
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Abstract
The invention discloses a selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol (amine) and a synthetic method thereof; belonging to the technical field of organic chemical synthesis; the method comprises the following steps: 1,2-diphenyl-1,2-ethylenediamine analogue reacts with N-butyllithium, then reacts with dichloro-N, N-diisopropylphosphoramidite or dimethyl phosphoroamidite chloride, and is oxidized by sulfur powder or selenium powder to prepare 1,2-diphenylamines catalyst; phosphorus trichloride and triethylamine are reacted under the common action of diisopropylamine or dimethylamine, chiral 1,2-diphenyl-1,2-glycol and selenium powder or sulfur powder to produce 1,2-diphenyl alcohol catalyst. The catalyst prepared by the invention has excellent catalytic activity.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol (amine) and a synthesis method thereof.
Background
One of the core research activities in the field of asymmetric catalysis is the continuous development of new phosphorus ligands aimed at increasing efficiency and selectivity to meet the ever-increasing needs of the academic and industrial sectors. Although the use of a number of chiral phosphorus ligands has been reported, the modification of existing ligands or the improvement of the development properties of novel chiral ligands continues to attract interest to synthetic chemists. Chiral diols are structural motifs which are common in a variety of important natural products and have also proven to be valuable chiral ligands and adjuvants in the context of stereo-electrochemical organic synthesis. Enantioselective synthesis of chiral diols remains an exciting subject. One of the most successful methods is the enantioselective reduction of prochiral diketones with chiral catalysts and reagents. Currently, a large number of reducing agents and chiral catalysts are being developed (Angew Chem Int Ed, 1998,37,1986.). The aryl alcohol skeleton is an important component of the catalyst in the modern organic synthesis field, common binaphthol skeleton, spiro phenol skeleton, TADDOL skeleton and the like are included, and compared with the common catalyst skeleton, the development of the catalyst of 1,2-diphenyl-1,2-ethylene glycol skeleton is less.
Similarly, 1,2-diphenyl-1,2-diamine (diphenylethylene diamine) has long been used as a ligand in metal chelate studies due to its C2 symmetry. Relevant literature (e.g., j. Am. chem. Soc. 1959, 81, 4464; rec. Trav. Chint. 1940, 59, 173, E.J. Corey (Tetrahedron Lett.1997, 38, 8631-8634) concluded that the enantiomers of this diamine have been widely used in new reagents and catalysts for enantioselective synthesis for example, a number of highly enantioselective articles have been published such as Diels-Alder, aldol condensation, carbo-and propargylation, dihydroxylation and olefin epoxidation, electrophiles of alkenoates etc. likewise, chiral 1,2-diphenyl-1,2-ethylenediamine has been used as a resolving agent for racemates, for example Brunner (Angel. Chem. 1994, 106, 130.) chiral 2 zxft 8652-diphenyl-1,2-ethylenediamine has been used to resolve chiral binaphthol derivatives (R, R) -3579 zzft 3579-diphenylethylenediamine (see also: J. chem. Soc. Perkin Trans. 1994, 2, 57-64.) meanwhile, chiral 1,2-diphenyl-1,2-ethylenediamine can also be used as a chiral catalyst to form a complex with palladium (see: angew. Chem. Int. Ed. 1996, 35, 1344-1346.). Scott. E. Denmark (see: J. Org. Chem. 1999, 64, 1958-1967.) detailed reports have been made on 1,2-diphenylphosphatides catalysts, but only oxides of 1,2-diphenyl-based catalysts are limited, and studies on sulfur and selenides of 1,2-diphenyl-based catalysts are less reported.
The prior art, for example, publication No. CN 103433073A discloses a metal organic framework catalyst grafted with (1R, 2R) -1,2-diphenylethylenediamine, a preparation method and application thereof; wherein the metal organic framework structure material is an MIL-101 material; the preparation method of the catalyst comprises the following steps: dehydrating MIL-101 material at 150 ℃ in vacuum for 12h, cooling to room temperature, quickly pouring the dehydrated MIL-101 into anhydrous toluene, then adding (1R, 2R) -1,2-diphenylethylenediamine, refluxing and stirring at 110 ℃ for 12h, filtering, washing with ethanol, and drying at room temperature to obtain the grafting catalyst. The catalyst has the advantages of environmental friendliness, mild reaction conditions, high efficiency and good stability.
Disclosure of Invention
The invention aims to provide a method for synthesizing a selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol (amine) with excellent catalytic activity.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol (amine) has a structural formula selected from one of the following:
of these, R, R 1 Each independently selected from H, C 1 ~C 12 Alkyl, substituted C 1 ~C 12 Alkyl, phenyl or benzyl.
In another preferred embodiment of the present invention, R is selected from methyl, ethyl, propyl, isopropyl, phenyl or the benzyl group; the R is 1 Selected from methyl, ethyl, propyl, isopropyl or phenyl.
In another preferred embodiment of the invention, R is selected from methyl or benzyl; said R is 1 Independently selected from methyl or isopropyl.
The invention also discloses a preparation method of the selenium/sulfur compound based on 1,2-diaryl-1,2-ethanediol (amine), which comprises the following steps:
reacting 1,2-diphenyl-1,2-ethylenediamine analogue with N-butyllithium, reacting with dichloro-N, N-diisopropylphosphoramidite or dimethylphosphoryl chloride, and oxidizing by sulfur powder or selenium powder to obtain a selenium/sulfur compound shown in formula (I);
phosphorus trichloride and triethylamine are reacted under the combined action of an amine compound, chiral 1,2-diphenyl-1,2-ethylene glycol and selenium powder or sulfur powder to generate a selenium/sulfur compound shown in a formula (II);
the 1,2-diphenyl-1,2-ethylenediamine analogue has the structural formula as follows:
；
the structural formula of the amine compound is as follows:
；
of these, R, R 1 Each independently selected from H, C 1 ~C 12 Alkyl, substituted C 1 ~C 12 Alkyl, phenyl or benzyl.
Further, in another preferred embodiment of the present invention, the specific preparation method of the selenium/sulfur compound represented by formula (i) is: dissolving 1,2-diphenylamine analogue in a solvent, cooling the system, slowly adding N-butyllithium, heating to room temperature, stirring for reaction, cooling, adding dichloro-N, N-diisopropylphosphoramidite or dimethylphosphorylamine chloride into the system, heating to room temperature, stirring, adding sulfur powder or selenium powder, continuing to react, distilling under reduced pressure, and purifying to obtain 1,2-diphenylamine compound.
Further, in another preferred embodiment of the present invention, the molar ratio of 1,2-diphenylamine analog, dichloro-N, N-diisopropylphosphoramidite and selenium powder is 1:0.5 to 1.5:2~5.
Further, in another preferred embodiment of the present invention, the molar ratio of 1,2-diphenylamine analogue, dimethyl phosphoroamidite chloride to sulfur powder is 1:0.75 to 1.5:2~5.
Further, in another preferred embodiment of the present invention, the ratio of 1,2-diphenylamine analog, solvent and n-butyllithium is 0.75 to 1mmol:4 to 10mL:0.1 to 0.5mL.
Further, in another preferred embodiment of the present invention, the specific preparation method of the selenium/sulfur compound represented by formula (ii) is: dissolving phosphorus trichloride in a solvent, cooling, slowly adding triethylamine, heating the system to room temperature after reaction, then adding an amine compound to perform stirring reaction, then adding chiral 1,2-diphenyl-1,2-ethylene glycol, continuing stirring reaction, finally adding selenium powder or sulfur powder, continuing stirring reaction, filtering, distilling under reduced pressure, and purifying to obtain 1,2-diphenyl alcohol compound.
Further, in another preferred embodiment of the invention, the molar ratio of the chiral 1,2-diphenyl-1,2-glycol, the amine compound and the selenium powder is 1:0.5 to 2:2.5 to 5.5.
Further, in another preferred embodiment of the invention, the molar ratio of the chiral 1,2-diphenyl-1,2-ethylene glycol, the amine compound and the sulfur powder is 1:0.5 to 2:2.5 to 5.
Further, in another preferred embodiment of the invention, the chiral 1,2-diphenyl-1,2-ethylene glycol, phosphorus trichloride and the solvent are 0.5 to 1mmol:0.15 to 0.55mmol:5 to 20mL.
Further, in another preferred embodiment of the present invention, the solvent is at least one selected from dichloromethane, tetrahydrofuran and toluene.
Preferred embodiments of the present invention relate to selenium/sulfur based compounds of formula (but not limited to) selected from one of the following:
the invention also discloses application of the 1,2-diaryl-1,2-ethanediol (amine) -based selenium/sulfur compounds in catalyzing synthesis reaction of axial chiral sulfur-containing diphenyl derivatives.
Compared with the prior art, the invention has the following characteristics:
1) According to the method, synthesis of the chiral 1,2-diphenyl derived selenium/sulfur compound is realized for the first time by functionalizing hydrogen on 1,2-diphenyl substrate, and the prepared compound has good flexibility and controllability and has excellent catalytic activity;
2) The method adopts cheap and easily-purchased 1,2-diphenyl alcohol or amine substrate, the product is prepared by a one-pot method, and the reaction process avoids a complex synthetic route;
3) The method has diversified substrates, can synthesize 1,2-diphenyl compounds with various types and different substituents, and has excellent catalytic activity in the catalytic axial chiral sulfur-containing diphenyl derivative synthesis reaction.
Drawings
FIG. 1 shows the preparation of Compound 1 of example 1 1 H nuclear magnetic resonance spectroscopy;
FIG. 2 is a drawing showing the preparation of Compound 1 in example 1 13 C nuclear magnetic resonance spectroscopy;
FIG. 3 is a drawing showing the preparation of Compound 2 in example 2 1 H nuclear magnetic resonance spectroscopy;
FIG. 4 shows Compound 2 of example 2 13 C nuclear magnetic resonance spectroscopy;
FIG. 5 shows the preparation of Compound 3 in example 3 1 H nuclear magnetic resonance spectroscopy;
FIG. 6 shows the preparation of Compound 3 in example 3 13 C nuclear magnetic resonance spectroscopy;
FIG. 7 shows the preparation of Compound 4 in example 4 1 H nuclear magnetic resonance spectroscopy;
FIG. 8 shows the preparation of Compound 4 of example 4 13 C nuclear magnetic resonance spectroscopy;
FIG. 9 shows Compound 5 of example 5 1 H nuclear magnetic resonance spectroscopy;
FIG. 10 shows Compound 5 of example 5 13 C nuclear magnetic resonance spectroscopy;
FIG. 11 is a drawing showing the preparation of Compound 6 in example 6 1 H nuclear magnetic resonance spectroscopy;
FIG. 12 shows preparation of Compound 6 in example 6 13 C nuclear magnetic resonance spectroscopy;
FIG. 13 is a drawing showing the preparation of Compound 7 in example 7 1 H nuclear magnetic resonance spectroscopy;
FIG. 14 shows Compound 7 of example 7 13 C nuclear magnetic resonance spectroscopy;
FIG. 15 is a drawing of Compound 8 from example 8 1 H nuclear magnetic resonance spectroscopy;
FIG. 16 is a drawing of Compound 8 from example 8 13 C nuclear magnetic resonance spectroscopy;
FIG. 17 is a drawing of Compound 9 of example 9 1 H nuclear magnetic resonance spectroscopy;
FIG. 18 is a drawing of Compound 9 of example 9 13 C nuclear magnetic resonance spectroscopy;
FIG. 19 is a photograph of Compound 10 of example 10 1 H nuclear magnetic resonance spectroscopy;
FIG. 20 is a photograph of Compound 10 of example 10 13 C nuclear magnetic resonance spectroscopy;
FIG. 21 shows examples of application of Compound 13 1 H nuclear magnetic resonance spectroscopy;
FIG. 22 shows examples of the use of Compound 13 13 C nuclear magnetic resonance spectroscopy;
FIG. 23 is an HPLC chromatogram of a racemic sample of Compound 13 in an application example;
FIG. 24 is an HPLC chromatogram of a chiral sample of Compound 13 in the application example.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention. The examples provided below serve as a guide for further modifications by a person skilled in the art and do not constitute a limitation of the invention in any way.
In another preferred embodiment of the present invention, the specific preparation method of 1,2-diphenylamines compound is: dissolving 1,2-diphenylamine analogue in a solvent, reducing the temperature of a system to-85 to-70 ℃, slowly adding N-butyllithium, heating to room temperature, stirring for reaction for 4 to 8h, reducing the temperature of the system to-85 to-70 ℃, adding dichloro-N, N-diisopropylphosphoramidite or dimethylphosphide chloride into the system for reaction, heating to room temperature, stirring for reaction for 20 to 50min, adding sulfur powder or selenium powder for oxidation for 1 to 3h, carrying out reduced pressure distillation, and purifying by column chromatography to obtain 1,2-diphenylamine compound, wherein the yield is 27.5 to 79%. The specific preparation route is as follows:
in another preferred embodiment of the present invention, 1,2-diphenyl alcohol compound is prepared by the following specific method: dissolving phosphorus trichloride in a solvent, cooling to a low temperature of 0~3 ℃, slowly adding triethylamine, reacting for 3-7min, heating the system to room temperature, adding diisopropylamine or dimethylamine, stirring for reacting for 3-6h, adding chiral 1,2-diphenyl-1,2-ethylene glycol, continuously stirring for reacting for 10-15h, finally adding selenium powder or sulfur powder, continuously stirring for reacting for 2-4h, filtering, distilling under reduced pressure, and purifying by column chromatography to obtain 1,2-diphenyl alcohol compounds, wherein the yield is 25-65%. The specific preparation route is as follows:
the invention also discloses a selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol (amine), which comprises a compound 3 and a compound 7, wherein the weight ratio of the compound 3 to the compound 7 is 1:0.25 to 0.65.
The compound 3 and the compound 7 are used together as a composite catalyst, and the weight ratio of the compound 3 to the compound 7 is 1: when the reaction temperature is 0.25 to 0.65, the asymmetric direct aldol condensation reaction of the p-nitrobenzaldehyde and the acetone has better catalytic effect.
In the present embodiment, it is to be noted that, nuclear magnetic resonance spectrum of compound ( 1 H NMR、 13 C NMR) was determined from Bruker AVANCE III HD 400 and the solvent was deuterated chloroform. Chemical shifts (δ) are quoted in ppm units, with tetramethylsilane as the internal standard, and the multiplicities are: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet.
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
a preparation method of selenium/sulfur compounds based on 1,2-diaryl-1,2-ethylene glycol (amine), wherein the preparation of the compound 1: the specific preparation route is as follows:
dissolving 300mg of chiral N, N' -dimethyl-1,2-diphenyl-1,2-ethylenediamine (1.25 mmol, 1.0 equiv) in 12mL of tetrahydrofuran, cooling the system to-78 ℃, dropwise adding 1.0mL of N-butyllithium (2.5M, 2.50mmol, 2.0 equiv), stirring at room temperature for reaction for 30 minutes, cooling the system to-78 ℃, dropwise adding 0.23mL of dichloro-N, N-diisopropylphosphoramidite (1.25 mmol, 1.0 equiv) into the system for reaction, slowly heating the system to room temperature, stirring for reaction for 30 minutes, finally adding 296mg of selenium powder (3.75 mmol, 3.0 equiv) for oxidation reaction for 2 hours at room temperature, and then carrying out reduced pressure distillation and column chromatography purification to prepare 1,2-diphenylamine compound 1; the yield was 47%.
1 (400 MHz, CDCl 3 ) δ 7.31-7.24 (m, 6H), 7.17 (s, 2H), 7.07-7.03 (m, 2H), 4.21 (dd, J = 8.7, 1.3 Hz, 1H), 4.16-3.94 (m, 2H), 3.82 (d, J = 8.7 Hz, 1H), 2.87-2.00 (m, 6H), 1.45 (t, J = 6.7 Hz, 12H); as shown in FIG. 1;
13 C NMR (101 MHz, CDCl 3 ) δ 138.22, 138.17, 137.85, 137.74, 128.78, 128.64, 128.52, 128.17, 128.05, 127.94, 71.93, 71.84, 71.73, 71.65, 47.78, 31.69, 31.63, 28.50, 28.42, 23.42; as shown in fig. 2.
Example 2:
a preparation method of selenium/sulfur compounds based on 1,2-diaryl-1,2-ethylene glycol (amine), wherein the specific preparation route of the compound 2 is as follows:
dissolving 400mg of chiral N, N' -dimethyl-1,2-diphenyl-1,2-ethylenediamine (1.66 mmol, 1.0 equiv) in 17mL of tetrahydrofuran, cooling the system to-78 ℃, dropwise adding 1.3mL of N-butyllithium (2.5M, 3.33mmol, 2.0 equiv), stirring at room temperature for reaction for 30min, cooling the system to-78 ℃, dropwise adding 0.31mL of dichloro-N, N-diisopropylphosphoramidite (1.66 mmol, 1.0 equiv) into the system for reaction, slowly heating the system to room temperature, stirring for reaction for 30min, finally adding 160mg of sulfur powder (4.99 mmol, 3.0 equiv) for oxidation reaction for 2h at room temperature, and then carrying out reduced pressure distillation and column chromatography purification to prepare 1,2-diphenylamine compound 2; the yield was 45%.
1 H NMR (400 MHz, CDCl 3 ) δ 7.41-7.18 (m, 6H), 7.05-6.95 (m, 4H), 4.04 (dd, J = 8.7, 1.4 Hz, 1H), 3.80 (t, J = 8.6 Hz, 3H), 2.74-2.18 (m, 6H), 1.55-1.13 (m, 12H); as shown in fig. 3;
13 C NMR (101 MHz, CDCl 3 ) δ 138.57, 138.52, 138.47, 138.36, 128.60, 128.58, 128.50, 128.10, 128.02, 127.86, 71.94, 71.85, 71.76, 47.14, 31.02, 30.97, 28.54, 28.47, 23.21; as shown in fig. 4.
Example 3:
a preparation method of selenium/sulfur compounds based on 1,2-diaryl-1,2-ethylene glycol (amine), wherein the specific preparation route of the compound 3 is as follows:
150mg of chiral 1,2-diphenyl-N1, N2-bis (benzyl) -1,2-ethylenediamine (0.38 mmol, 1.0 equiv) is dissolved in 2mL of tetrahydrofuran, 0.3mL of N-butyllithium (2.5M, 0.76mmol, 2.0 equiv) is added dropwise after the system is cooled to-78 ℃, after stirring reaction is carried out for 30min at room temperature, the system is cooled to-78 ℃ again, then 0.07mL of dichloro-N, N-diisopropylphosphoramidite (0.38 mmol, 1.0 equiv) is added dropwise to the system for reaction, the system is slowly heated to room temperature and stirred for reaction for 30min, and finally 91mg of selenium powder (1.15 mmol, 3.0 equiv) is added at room temperature for oxidation reaction for 2h, and then reduced pressure distillation and column chromatography purification are carried out to prepare 1,2-diphenylamine compound 3; the yield was 42%.
1 H NMR (400 MHz, CDCl 3 ) δ 7.45-7.30 (m, 2H), 7.23-6.94 (m, 16H), 6.93-6.86 (m, 2H), 4.37-4.26 (m, 4H), 4.19-3.88 (m, 2H), 1.43 (d, J = 6.9 Hz, 6H), 1.35 (d, J = 7.0 Hz, 6H); as shown in fig. 5;
13 C NMR (101 MHz, CDCl 3 ) δ 139.08, 138.99, 137.87, 137.84, 137.68, 137.60, 135.97, 130.82, 129.51, 128.47, 128.38, 128.02, 127.97, 127.93, 127.79, 127.63, 127.25, 126.68, 70.18, 70.11, 69.41, 69.30, 49.25, 49.17, 47.92, 47.46, 47.37, 24.18, 23.67; as shown in fig. 6.
Example 4:
a preparation method of selenium/sulfur compounds based on 1,2-diaryl-1,2-ethylene glycol (amine), wherein the specific preparation route of the compound 4 is as follows:
dissolving 100mg of chiral 1,2-diphenyl-N1, N2-bis (benzyl) -1,2-ethylenediamine (0.26 mmol, 1.0 equiv) in 1mL of tetrahydrofuran, cooling the system to-78 ℃, adding 0.2 mL N-butyllithium (2.5M, 0.51mmol, 2.0 equiv) dropwise, stirring at room temperature for reaction for 30min, cooling the system to-78 ℃, adding 0.05mL of dichloro-N, N-diisopropylphosphoramidite (0.26 mmol, 1.0 equiv) dropwise into the system for reaction, slowly heating the system to room temperature, stirring for reaction for 30min, finally adding 25mg of sulfur powder (0.71 mmol, 3.0 equiv) at room temperature, oxidizing for 2h, distilling under reduced pressure, purifying by column chromatography, and obtaining 1,2-diphenylamine compound 4; the yield was 29%.
1 H NMR (400 MHz, CDCl 3 ) δ 7.34-7.31 (m, 2H), 7.25-6.75 (m, 18H), 4.43 (t, J = 14.0 Hz, 1H), 4.26 (dd, J = 7.7, 5.8 Hz, 1H), 4.14-3.99 (m, 5H), 3.89 (t, J = 14.4 hz, 1h), 1.48 (d, J = 6.8 Hz, 6H), 1.39 (dd, J = 9.4, 6.6 Hz, 6H); as shown in fig. 7;
13 C NMR (101 MHz, CDCl 3 ) δ 139.35, 139.26, 138.31, 138.27, 138.13, 138.06, 135.96, 135.93, 130.64, 129.29, 128.44, 128.37, 127.97, 127.91, 127.89, 127.85, 127.82, 127.78, 127.56, 127.18, 126.59, 70.30, 70.22, 70.30, 70.30, 6258 zxft 58, 48.12, 47.25, 70.30, 6258 zxft 6223.46; as shown in fig. 8.
Example 5:
a preparation method of selenium/sulfur compounds based on 1,2-diaryl-1,2-ethylene glycol (amine), wherein the specific preparation route of the compound 5 is as follows:
dissolving 500mg of chiral N, N' -dimethyl-1,2-diphenyl-1,2-ethylenediamine (2.08 mmol, 1.0 equiv) in 8mL of tetrahydrofuran, cooling the system to-78 ℃, adding 1.7mL of N-butyl lithium (2.5M, 4.16mmol, 2.0 equiv) dropwise, stirring at room temperature for reaction for 30min, cooling the system to-78 ℃, adding 0.24mL of dimethyl ammonium chloride (2.08 mmol, 1.0 equiv) dropwise for reaction, slowly heating the system to room temperature, stirring for reaction for 30min, finally adding 493mg of selenium powder (6.24 mmol, 3.0 equiv) at room temperature for oxidation for 2h, and then carrying out reduced pressure distillation and column chromatography purification to prepare 1,2-diphenylamine compound 5; the yield was 75%.
1 H NMR (400 MHz, CDCl 3 ) δ 7.28 (dt, J = 6.3, 2.4 Hz, 6H), 7.17-6.92 (m, 4H), 4.20 (d, J = 8.6 Hz, 1H), 3.81 (d, J = 8.6 Hz, 1H), 3.01 (d, J = 11.5 Hz, 6H), 2.35 (d, J = 10.4 Hz, 3H), 2.26 (d, J = 14.5 Hz, 3H); as shown in fig. 9;
13 C NMR (101 MHz, CDCl 3 ) δ 138.15, 137.96, 128.66, 128.58, 128.38, 128.30, 128.18, 127.92, 72.30, 71.78, 71.70, 37.96, 37.91, 31.63, 28.37, 28.29; as shown in fig. 10.
Example 6:
a preparation method of selenium/sulfur compounds based on 1,2-diaryl-1,2-ethylene glycol (amine), wherein the specific preparation route of the compound 6 is as follows:
dissolving 500mg of chiral N, N' -dimethyl-1,2-diphenyl-1,2-ethylenediamine (2.08 mmol, 1.0 equiv) in 8mL of tetrahydrofuran, cooling the system to-78 ℃, then adding 1.7mL of N-butyllithium (2.5M, 4.16mmol, 2.0 equiv) dropwise, stirring at room temperature for reaction for 30min, cooling the system to-78 ℃, then adding 0.24mL of dimethyl phosphoroamine chloride (2.08 mmol, 1.0 equiv) dropwise into the system for reaction, slowly heating the system to room temperature, stirring for reaction for 30min, finally adding 200mg of sulfur powder (6.24 mmol, 3.0 equiv) at room temperature for oxidation reaction for 2h, and then carrying out reduced pressure distillation and column chromatography purification to prepare 1,2-diphenylamine compound 6; the yield was 72%.
1 H NMR (400 MHz, CDCl 3 ) δ 7.30-7.27 (m, 6H), 7.23-6.97 (m, 4H), 4.07 (d, J = 8.6 Hz, 1H), 3.83 (d, J = 8.6 Hz, 1H), 2.98 (d, J = 11.1 Hz, 6H), 2.35 (d, J = 10.1 Hz, 3H), 2.28 (d, J = 13.6 Hz, 3H); as shown in fig. 11;
13 C NMR (101 MHz, CDCl 3 ) δ 138.43, 138.36, 128.65, 128.59, 128.30, 128.26, 128.17, 127.93, 72.28, 72.20, 71.88, 71.78, 37.85, 37.80, 31.11, 31.06, 28.46, 28.40; as shown in fig. 12.
Example 7:
the preparation method of the selenium/sulfur compound based on 1,2-diaryl-1,2-glycol (amine), wherein the specific preparation route of the compound 7 is as follows:
0.12mL of phosphorus trichloride (1.40 mmol, 1.0 equiv) was dissolved in 5.6mL of dichloromethane, the system was cooled to a low temperature of 0 ℃ and 0.93mL of triethylamine (7.00 mmol, 5.0 equiv) was added dropwise thereto, the system was warmed to room temperature after 5min of reaction, and 0.20mL of diisopropylamine (1.40 mmol, 1.0 equiv) was added, followed by stirring for 5h of reaction. 0.30g of chiral 1,2-diphenylglycol (1.40 mmol, 1.0 equiv) is added into the system at room temperature, stirred and reacted for 12 hours, 322mg of selenium powder (4.2 mmol, 3.0 equiv) is added at room temperature, and stirring and reaction are continued for 2 hours. Then carrying out reduced pressure distillation and column chromatography purification to obtain 1,2-diphenyl alcohol compound 7; the yield was 58%.
1 H NMR (400 MHz, CDCl 3 ) δ 7.49-7.41 (m, 2H), 7.41-7.30 (m, 6H), 7.20-7.12 (m, 2H), 5.49 (d, J = 9.3 Hz, 1H), 5.14 (dd, J = 9.3, 2.1 Hz, 1H), 4.12 (dpJ = 20.8, 6.9 Hz, 2H), 1.47 (dd, J = 8.9, 6.9 Hz, 12H); as shown in fig. 13;
13 C NMR (101 MHz, CDCl 3 ) δ 135.56, 135.48, 134.48, 134.35, 129.22, 129.17, 128.85, 128.02, 126.60, 87.01, 86.98, 83.65, 83.63, 48.93, 48.88, 23.11, 23.08, 22.91, 22.88; as shown in fig. 14.
Example 8:
a preparation method of selenium/sulfur compounds based on 1,2-diaryl-1,2-ethylene glycol (amine), wherein the specific preparation route of the compound 8 is as follows:
0.12mL of phosphorus trichloride (1.40 mmol, 1.0 equiv) was dissolved in 5.6mL of dichloromethane, the system was cooled to a low temperature of 0 ℃ and 0.93mL of triethylamine (7.00 mmol, 5.0 equiv) was added dropwise thereto, the system was warmed to room temperature after 5min of reaction, and 0.20mL of diisopropylamine (1.40 mmol, 1.0 equiv) was added, followed by stirring for 5h of reaction. 0.30g of chiral 1,2-diphenylglycol (1.40 mmol, 1.0 equiv) is added into the system at room temperature, stirred and reacted for 12 hours, 134mg of sulfur powder (4.2 mmol, 3.0 equiv) is added at room temperature, and stirring and reaction are continued for 2 hours. Then carrying out reduced pressure distillation and column chromatography purification to obtain 1,2-diphenyl alcohol compound 8; the yield was 60%.
1 H NMR (400 MHz, CDCl 3 ) δ 7.48-7.30 (m, 8H), 7.20-7.09 (m, 2H), 5.43 (d, J = 9.2 Hz, 1H), 5.07 (dd, J = 9.2, 2.6 Hz, 1H), 3.95 (dp, J = 20.8, 6.9 Hz, 2H), 1.46 (dd, J = 15.5, 6.8 Hz, 12H); as shown in fig. 15;
13 c NMR (101 MHz, CDCl 3) delta 135.83, 135.76, 134.93, 134.81, 129.16, 129.12, 128.83, 127.72, 126.47, 87.13, 87.11, 83.73, 83.70, 48.22, 48.17, 22.84, 22.81, 22.64, 22.62; as shown in fig. 16.
Example 9:
a preparation method of selenium/sulfur compounds based on 1,2-diaryl-1,2-ethylene glycol (amine), wherein the specific preparation route of the compound 9 is as follows:
0.16mL of phosphorus trichloride (1.87 mmol, 1.0 equiv) was dissolved in 7.5mL of dichloromethane, the system was cooled to a low temperature of 0 ℃ and 1.40mL of triethylamine (9.34 mmol, 5.0 equiv) was added dropwise thereto, the system was allowed to warm to room temperature after 5min of reaction, and 0.05mL of dimethylamine (1.87 mmol, 1.0 equiv) was added, followed by stirring for 5h of reaction. 0.40g of chiral 1,2-diphenylglycol (2.58 mmol, 1.0 equiv) is added into the system at room temperature, stirred and reacted for 12 hours, 222mg of selenium powder (5.61 mmol, 3.0 equiv) is added at room temperature, and stirring and reaction are continued for 2 hours. Then carrying out reduced pressure distillation and column chromatography purification to obtain 1,2-diphenyl alcohol compound 9; the yield was 30%.
1 H NMR (400 MHz, CDCl 3 ) δ 7.44-7.30 (m, 8H), 7.23-7.13 (m, 2H), 5.36 (d, J = 9.2 Hz, 1H), 5.13 (dd, J = 9.2, 2.3 Hz, 1H), 3.03 (d, J = 11.9 Hz, 6H); as shown in fig. 17;
13 c NMR (101 MHz, CDCl 3) delta 135.29, 135.21, 134.41, 134.29, 129.40, 129.34, 128.94, 128.90, 127.54, 126.58, 87.78, 87.75, 84.51, 84.49, 37.96, 37.91; as shown in fig. 18.
Example 10:
the preparation method of the selenium/sulfur compound based on 1,2-diaryl-1,2-glycol (amine), wherein the specific preparation route of the compound 10 is as follows:
0.16mL of phosphorus trichloride (1.87 mmol, 1.0 equiv) was dissolved in 7.5mL of dichloromethane, the system was cooled to a low temperature of 0 ℃ and 1.40mL of triethylamine (9.34 mmol, 5.0 equiv) was added dropwise thereto, the system was allowed to warm to room temperature after 5min of reaction, and 0.05mL of dimethylamine (1.87 mmol, 1.0 equiv) was added, followed by stirring for 5h of reaction. 0.40g of chiral 1,2-diphenylglycol (2.58 mmol, 1.0 equiv) was added to the system at room temperature, and the mixture was stirred and reacted for 12 hours, and 90mg of sulfur powder (5.61 mmol, 3.0 equiv) was added at room temperature, and the reaction was continued for 2 hours under stirring. Then carrying out reduced pressure distillation and column chromatography purification to obtain 1,2-diphenyl alcohol compound 10; the yield was 32%.
1 H NMR (400 MHz, CDCl 3 ) δ 7.41-7.30 (m, 1H), 7.25-7.16 (m, 0H), 5.38 (d, J = 9.2 Hz, 0H), 5.19 (dd, J = 9.3, 1.8 Hz, 0H), 3.06 (d, J = 12.3 Hz, 1H); as shown in fig. 19;
13 C NMR (101 MHz, CDCl 3 ) δ 135.57, 135.49, 134.83, 134.71, 129.36, 129.30, 128.93, 128.88, 127.37, 126.54, 87.72, 87.70, 84.54, 84.51, 37.77, 37.72; as shown in fig. 20.
Example 11:
a preparation method of selenium/sulfur compounds based on 1,2-diaryl-1,2-ethylene glycol (amine) comprises a compound 3 and a compound 7, wherein the weight ratio of the compound 3 to the compound 7 is 1:0.35.
example 12:
different from the embodiment 11, the preparation method of the selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol (amine) comprises a compound 4 and a compound 7.
Example 13:
different from the embodiment 11, the preparation method of the selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol (amine) comprises a compound 5 and a compound 7.
Comparative example 1:
the chiral sulfur/selenium compound of 1,1' -bi-2-naphthol skeleton with the structural formula shown below was used as comparative example 1;
comparative example 2:
the chiral sulfur/selenium compound of 1,1' -bi-2-naphthol skeleton with the structural formula shown below was used as comparative example 2;
application example:
catalyzing the reaction of the axial chiral sulfur-containing diphenyl derivative by using the prepared 1,2-diphenyl alcohol compound 7; the catalytic reaction route is as follows:
compound 11 (cas No. 2414175-61-2), compound 12 (cas No. 2376073-20-8), 1,2-diphenylol compound 7 and (C) (anhydrous anaerobic condition)R) Adding Chiral Phosphoric Acid (CPA) into a dried reaction tube, adding 0.5mL ultra-dry dichloromethane into the reaction tube at the low temperature of-40 ℃, reacting for 24 hours in an argon atmosphere, heating the system to-30 ℃, continuing reacting for 4 hours, heating the reaction to-20 ℃ again, reacting for 10 hours, and carrying out column chromatography purification on the reaction system to obtain the axial chiral sulfur-containing diphenyl derivative 13.
1 (400 MHz, CDCl 3 ) δ 7.48 (m, 2H), 7.34 (m, 1H), 7.22-7.07 (m, 4H), 6.91 (dd, J = 8.6, 1.9 Hz, 1H), 6.49 (dd, J = 8.6, 1.9 Hz, 1H), 6.04-5.85 (m, 1H), 4.70 (s, 1H), 2.73 (tt, J = 6.9, 3.5 Hz, 1H), 2.47 (d, J = 2.2 Hz, 6H), 1.13 (dd, J= 6.6, 2.1 Hz, 6H); as shown in fig. 21;
13 C NMR (101 MHz, CDCl 3 ) δ 153.52, 152.62, 149.80, 142.50, 132.73, 131.65, 131.25, 129.94, 129.15, 128.80, 128.72, 127.03, 126.72, 114.73, 112.08, 108.54, 30.51, 24.12, 23.94, 22.13; as shown in fig. 22.
HPLC separation of enantiomers, chiralcel columns AD-H, 30 oC, n-hexane i-PrOH = 85, 1 mL/min, secondary retention time 6.85 min, primary retention time 8.01 min, er =45.3, as shown in fig. 23, 24.
Test example 1:
test for catalytic Performance
1. Test of catalytic axial chiral sulfur-containing bisphenyl derivative Synthesis reaction
Other steps are the same as the application examples, only the kinds of the compounds (the compounds in examples 1 to 13 and comparative examples 1 to 2) are changed, and Yield and ee value (enantioselectivity) of the axial chiral sulfur-containing bisphenyl derivative are shown in Table 1.
TABLE 1 test results of selenium/sulfur compounds on synthetic reaction of chiral sulfur-containing diphenyl derivatives of shaft
As can be seen from Table 1, the yield of asymmetric direct aldol condensation reaction of o-nitrobenzaldehyde and acetone catalyzed by the selenium/sulfur compound in examples 1-10 is not lower than 57%, the ee value is not lower than 7%, the yield and ee value of the selenium/sulfur compound in examples 1-10 are higher than those in comparative examples 1-2 compared with examples 1-10 and comparative examples 1-2, which shows that the chiral 1,2-diphenyl derived selenium/sulfur compound prepared by functionalizing hydrogen on 1,2-diphenyl substrate has excellent catalytic effect on the synthesis reaction of chiral sulfur-containing diphenyl derivatives and the reaction rate is fast; the yield of asymmetric direct aldol condensation reaction of the selenium/sulfur compound p-nitrobenzaldehyde and acetone in examples 11-13 is not lower than 82%, the ee value is not lower than 21%, and compared with examples 3-5, 7 and 11-13, the yield and ee value of the selenium/sulfur compound in example 13 are higher than those in examples 3-5, 7, 11 and 12, which shows that the compound 5 and the compound 7 have better catalytic activity for the synthesis reaction of chiral sulfur-containing diphenyl derivatives.
(2) The compound 5 and the compound 7 are used together as a composite catalyst, and the weight ratio of the compound 5 and the compound 7 influences the synthesis reaction of the chiral sulfur-containing diphenyl derivative of the shaft;
the weight ratio of compound 5 to compound 7 was 1:0.15, 1:0.25, 1:0.45, 1:0.65, 1:0.75 of the selenium/sulfur compounds are respectively marked as catalyst A, catalyst B, catalyst C, catalyst D and catalyst E, and the influence of the synthetic reaction on the chiral sulfur-containing diphenyl derivative is tested according to the test method, and the test results are shown in Table 2.
TABLE 2 test results of catalysts for synthetic reaction of chiral sulfur-containing bisphenyl derivatives of shafts
As can be seen from table 2, the yield of the axial chiral sulfur-containing diphenyl derivative synthesis reaction catalyzed by the catalyst B, the catalyst C and the catalyst D is not less than 86%, the ee value is not less than 29%, and the catalytic effects are all higher than those of the catalyst a and the catalyst B, which indicates that the weight ratio of the compound 5 to the compound 7 is 1: when the concentration is 0.25 to 0.65, the catalyst has a better catalytic effect on the synthetic reaction of the chiral sulfur-containing diphenyl derivative.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol/amine, the structural formula of which is selected from one of the following:
wherein R, R 1 Each independently selected from H, C 1 ~C 12 Alkyl, substituted C 1 ~C 12 Alkyl, phenyl or benzyl of (a);
each X is independently selected from Se or S.
2. The selenium/sulfur compound of claim 1 based on 1,2-diaryl-1,2-ethylene glycol/amine, wherein: r is selected from methyl, ethyl, propyl, isopropyl, phenyl or benzyl; said R is 1 Selected from methyl, ethyl, propyl, isopropyl or phenyl.
3. The selenium/sulfur compound of claim 1 based on 1,2-diaryl-1,2-ethylene glycol/amine, wherein: r is selected from methyl or benzyl; the R is 1 Selected from methyl or isopropyl.
4. The preparation method of the selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol/amine in claim 1, comprising the following steps:
reacting 1,2-diphenyl-1,2-ethylenediamine analogue with N-butyllithium, reacting with dichloro-N, N-diisopropylphosphoramidite or dimethylphosphoryl chloride, and oxidizing by sulfur powder or selenium powder to obtain a selenium/sulfur compound shown in formula (I);
phosphorus trichloride and triethylamine are reacted under the combined action of an amine compound, chiral 1,2-diphenyl-1,2-ethylene glycol and selenium powder or sulfur powder to generate a selenium/sulfur compound shown in a formula (II);
the 1,2-diphenyl-1,2-ethylenediamine analogue has the structural formula:
；
the structural formula of the amine compound is as follows:
；
of these, R, R 1 Each independently selected from H, C 1 ~C 12 Alkyl, substituted C 1 ~C 12 Alkyl, phenyl or benzyl.
5. The method for preparing the selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol/amine according to claim 4, which is characterized in that: the specific preparation method of the selenium/sulfur compound shown in the formula (I) comprises the following steps: 1,2-diphenyl-1,2-ethylenediamine analogue is dissolved in a solvent, after the system is cooled, N-butyl lithium is slowly added, the temperature is raised to room temperature, stirring reaction is carried out, the temperature is lowered, dichloro-N, N-diisopropylphosphoramidite or dimethyl phosphoroamine chloride is added into the system for reaction, the temperature is raised to room temperature, stirring is carried out, sulfur powder or selenium powder is added for continuous reaction, reduced pressure distillation and purification are carried out, and the selenium/sulfur compound is obtained.
6. The method of claim 5 for preparing selenium/sulfur based 1,2-diaryl-1,2-ethylene glycol/amine, wherein the method comprises the steps of: the 1,2-diphenyl-1,2-ethylenediamine analogue, the dichloro-N, N-diisopropylphosphoramidite and the selenium powder have the molar ratio of 1:0.5 to 1.5:2~5.
7. The method of claim 4 for preparing selenium/sulfur based 1,2-diaryl-1,2-ethylene glycol/amine comprising: the specific preparation method of the selenium/sulfur compound shown in the formula (II) comprises the following steps: dissolving phosphorus trichloride in a solvent, cooling, slowly adding triethylamine, heating the system to room temperature after reaction, then adding an amine compound to perform stirring reaction, then adding chiral 1,2-diphenyl-1,2-ethylene glycol, continuing stirring reaction, finally adding selenium powder or sulfur powder, continuing stirring reaction, filtering, distilling under reduced pressure, and purifying to obtain the 1,2-diphenyl alcohol compound.
8. The method for preparing the selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol/amine according to claim 4, which is characterized in that: the molar ratio of the chiral 1,2-diphenyl-1,2-glycol, the amine compound and the selenium powder is 1:0.5 to 2:2.5 to 5.5.
9. The method for preparing the selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol/amine according to claim 4, which is characterized in that: the structural formula of the selenium/sulfur compound is selected from one of the following formulas:
10. the application of a selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol/amine in catalyzing the synthesis reaction of axial chiral sulfur-containing diphenyl derivatives is characterized in that: the synthetic reaction of the axial chiral sulfur-containing diphenyl derivative comprises the following steps: compound 11 and compound 12 are catalyzed by the selenium/sulfur compound based on 1,2-diaryl-1,2-ethylene glycol/amine of claim 1 to produce compound 13;
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060014981A1 (en) * | 2002-10-11 | 2006-01-19 | Studiengesellschaft Kohle Mbh | Mixtures of chiral monophosphorus compounds used as ligand systems for asymmetric transition metal catalysis |
| CN111205328A (en) * | 2020-02-27 | 2020-05-29 | 上海交通大学 | Chiral sulfur/selenium compound and preparation method and application thereof |
| CN111285901A (en) * | 2020-02-27 | 2020-06-16 | 上海交通大学 | Chiral sulfur/selenium compound based on 1,1' -bi-2-naphthol framework and preparation method and application thereof |
| CN114478337A (en) * | 2022-01-30 | 2022-05-13 | 安徽泽升科技有限公司上海分公司 | Axial chiral sulfur-containing diaryl derivative and synthesis method thereof |
| CN114870892A (en) * | 2022-02-07 | 2022-08-09 | 上海交通大学 | Chiral binaphthyl catalyst and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060014981A1 (en) * | 2002-10-11 | 2006-01-19 | Studiengesellschaft Kohle Mbh | Mixtures of chiral monophosphorus compounds used as ligand systems for asymmetric transition metal catalysis |
| CN111205328A (en) * | 2020-02-27 | 2020-05-29 | 上海交通大学 | Chiral sulfur/selenium compound and preparation method and application thereof |
| CN111285901A (en) * | 2020-02-27 | 2020-06-16 | 上海交通大学 | Chiral sulfur/selenium compound based on 1,1' -bi-2-naphthol framework and preparation method and application thereof |
| CN114478337A (en) * | 2022-01-30 | 2022-05-13 | 安徽泽升科技有限公司上海分公司 | Axial chiral sulfur-containing diaryl derivative and synthesis method thereof |
| CN114870892A (en) * | 2022-02-07 | 2022-08-09 | 上海交通大学 | Chiral binaphthyl catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Chiral Diamines for a New Protocol To Determine the Enantiomeric Composition of Alcohols, Thiols, and Amines by 31P,1H,13C, and 19F NMR;Alexandre Alexakis et al.;《J. Org. Chem.》;19941231;第59卷(第12期);第3326-3334页 * |
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