CN114315894B - Chiral alpha-aryl phosphate, chiral alpha-aryl phosphine compound and synthesis thereof - Google Patents
Chiral alpha-aryl phosphate, chiral alpha-aryl phosphine compound and synthesis thereof Download PDFInfo
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Abstract
The invention discloses a chiral alpha-aryl phosphate, a chiral alpha-aryl phosphine compound and synthesis thereof, wherein the chiral alpha-aryl phosphate or the chiral alpha-aryl phosphine compound is a compound with a structure shown as a formula (II), a formula (IV) or a formula (V), an enantiomer structure and a raceme structure thereof;
wherein R is 1 、R 2 Is alkyl or aryl, ar' is aryl. The synthesis method comprises the following steps: under the inert gas atmosphere, adding a photosensitizer, a nickel catalyst, a chiral ligand, alkali and a reducing agent into an organic solvent for reaction; under the atmosphere of inert gas, adding alpha-bromophosphate and aryl halide into the reaction solution prepared in the previous step to react to obtain chiral alpha-aryl phosphate. The invention provides chiral alpha-bromophosphate and chiral alpha-aryl phosphine compounds with brand new structures and a synthesis method thereof.
Description
Technical Field
The invention relates to the technical field of chiral compound synthesis, and relates to a novel chiral alpha-aryl phosphate, a chiral alpha-aryl phosphine compound and a synthesis method thereof.
Background
Chiral phosphine-containing compounds are widely existing in natural products and pharmaceutically active molecules, are important chiral catalysts, greatly promote the development of organic chemistry, and play an important role in asymmetric catalysis. In recent years, with the continuous development and penetration of metal catalysts, the important role of chiral ligands in chemical synthesis is highlighted. Therefore, new ligand forms are continuously discovered, and the asymmetric synthesis of the ligand forms is further promoted in the fields of medicine, materials, fine chemical industry and the like.
However, the synthesis of chiral alpha-aryl phosphate is very difficult at present, and an efficient construction method is not available, so that no related report exists on the structure at present.
Therefore, the development of a novel synthesis method of chiral alpha-aryl phosphate is of great practical significance.
Disclosure of Invention
The invention provides a novel chiral alpha-aryl phosphate and a synthesis method thereof, and particularly provides a novel chiral alpha-aryl phosphate compound prepared by reduction cross coupling of aryl halide and alpha-bromophosphate under nickel/photo-redox catalysis, wherein the synthesis method has the advantages of high reaction efficiency, mild reaction, good atomic economy, excellent functional group compatibility and substrate universality and the like.
In order to achieve the above object, the present invention provides the following technical solutions:
a chiral alpha-aryl phosphate or chiral alpha-aryl phosphine compound, wherein the chiral alpha-aryl phosphate or chiral alpha-aryl phosphine compound is a compound with a structure shown as a formula (II), a formula (IV) or a formula (V), an enantiomer structure and a racemate structure thereof;
wherein R is 1 、R 2 Is alkyl or aryl, ar' is aryl.
As a preferable technical scheme:
a chiral α -aryl phosphate or chiral α -aryl phosphine compound as described above, said chiral α -aryl phosphate or chiral α -aryl phosphine compound being:
wherein Ph represents a phenyl group, ts represents a p-toluenesulfonyl group, i pr is isopropyl and Bz is benzoyl.
The invention also provides a method for synthesizing the chiral alpha-aryl phosphate, which comprises the following steps:
(1) Under the inert gas atmosphere, adding a photosensitizer, a nickel catalyst, a chiral ligand, alkali and a reducing agent into an organic solvent for reaction;
(2) Adding alpha-bromophosphate and aryl halide into the reaction liquid prepared in the step (1) in an inert gas atmosphere to react to obtain chiral alpha-aryl phosphate shown in a formula (II) or a formula (IV), wherein the structural formula of the alpha-bromophosphate is shown in a formula (I) or a formula (III);
the reaction equation is as follows:
the synthesis method has the advantages of simple steps, mild reaction conditions, high yield and low cost, and has great application prospect.
As a preferable technical scheme:
the photosensitizer is 2,4,5, 6-tetra (9-carbazolyl) -isophthalonitrile (4 CzIPN, the structural formula of which is shown below), terpyridyl ruthenium chloride hexahydrate Ru (bpy) according to the method 3 Cl 2 ·6H 2 O, tris (2- (4-trifluoromethylphenyl) pyridine) iridium fac-Ir (ppy) 3 Bis [2- (2, 4-difluorophenyl) -5-trifluoromethylpyridine][2-2' -bis (4-t-butylpyridine)]Ir (dF (CF) Ir bis (hexafluorophosphate) salt 3 )ppy) 2 (dtbbpy)]PF 6 One or a mixture of two or more of them;
the nickel catalyst is ethylene glycol dimethyl ether nickel bromide (NiBr) 2 DME), bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2 Palladium chloride (PdCl) 2 ) Copper triflate Cu (OTf) 2 Cobalt acetylacetonate Co (acac) 2 One or a mixture of two or more of them;
the chiral ligand is one or more than two of (1S, 2S) -N, N '-dimethyl-1, 2-diphenyl-1, 2-ethylenediamine, (4S, 4' S) -4,4 '-diisopropyl-4, 4',5 '-tetrahydro-2, 2' -bisoxazole, (4S, 4 'S) -4,4',5 '-tetrahydro-4, 4' -diphenyl-2, 2 '-bisoxazole, (S) - (-) -1,1' -bi-2-naphthylamine;
the alkali is one or more than two of cesium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium phosphate, lithium carbonate, sodium tert-butoxide, triethylamine, N, N, N ', N' -tetramethyl ethylenediamine (TMEDA) and tetramethyl guanidine (TMG);
the reducing agent is diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylate (HEH, its structural formula is shown below), zinc (Zn), manganese (Mn), magnesium (Mg), tetra-tri (dimethylamino) ethylene (TDEA), and pinacol biborate (B) 2 Pin 2 ) One or a mixture of two or more of them;
the organic solvent is one or more than two of 1, 4-dioxane, N' -dimethylacetamide, 1, 2-dichloroethane, tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile and acetone;
the reaction temperature of the reaction in the step (1) is 0-80 ℃ and the reaction time is 2-5 h;
the reaction in the step (2) is carried out for 0.5 to 48 hours under the condition of 0 to 80 ℃ under the irradiation of a blue light lamp with the weight of 5 to 40W;
the inert gas is nitrogen, helium, neon, argon, xenon, krypton, radon and the like;
the aryl halide is aryl iodide, and although the present invention only shows an example of aryl iodide, other aryl halides having similar properties to aryl iodide may be practically applied to the present invention, and the scope of the present invention is not limited thereto, and those skilled in the art may select aryl halides according to actual circumstances.
The method as described above, wherein the photosensitizer is 2,4,5, 6-tetra (9-carbazolyl) -isophthalonitrile (4 CzIPN);
the nickel catalyst is ethylene glycol dimethyl ether bromideNickel (NiBr) 2 ·DME)；
The chiral ligand is a ligand shown as a formula (L1);
the base is cesium carbonate;
the reducing agent is diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid (HEH);
the organic solvent is a mixture of 1, 4-dioxane and N, N' -dimethylacetamide;
the reaction temperature of the reaction in the step (1) is 15-30 ℃ and the reaction time is 30-60 min;
the reaction in the step (2) is carried out for 8-12 h under the conditions of illumination of a 30W blue light lamp and 15-30 ℃.
The method as described above, wherein the amount of the alpha-bromophosphate is 100 to 600% molar equivalent of the aryl halide;
the amount of the base is 50 to 500% molar equivalent of the aryl halide;
the amount of the reducing agent is 100-500% molar equivalent of the aryl halide;
the nickel catalyst is used in an amount of 1 to 200% molar equivalent of the aryl halide;
the dosage of the photosensitizer is 0.5-200% of the molar equivalent of aryl halide;
the chiral ligand is used in an amount of 1 to 200% molar equivalents of the aryl halide.
The method as described above, wherein the α -bromophosphate is used in an amount of 200% molar equivalent of the aryl halide;
the base is used in an amount of 150% molar equivalents of the aryl halide;
the reducing agent is used in an amount of 200% molar equivalents of the aryl halide;
the nickel catalyst is used in an amount of 10% molar equivalents of aryl halide;
the photosensitizer is used in an amount of 1% molar equivalent of the aryl halide;
the chiral ligand is used in an amount of 12% molar equivalents of the aryl halide.
The invention also provides a method for synthesizing the chiral alpha-aryl phosphine compound, which is used for reducing the chiral alpha-aryl phosphate shown in the formula (IV) to prepare the chiral alpha-aryl phosphine compound shown in the formula (V).
The method comprises the following specific operations: sequentially adding chiral alpha-aryl phosphate, triethylamine, degassed toluene and trichlorosilane in the formula (IV) in an inert gas atmosphere, uniformly mixing, and stirring at 110-130 ℃ for reacting for 20-28 hours to obtain the chiral alpha-aryl phosphine compound in the formula (V).
In addition, the invention also provides application of the chiral alpha-aryl phosphate or chiral alpha-aryl phosphine compound.
Said invention has the following advantages or beneficial effects:
the invention provides chiral alpha-bromophosphate and chiral alpha-aryl phosphine compound with brand new structure, provides a new direction for researching chiral phosphine-containing compound, and simultaneously provides a method for synthesizing chiral alpha-bromophosphate and chiral alpha-aryl phosphine compound with brand new structure, which particularly realizes reduction cross coupling of aryl halide and alpha-bromophosphate under nickel/photo-redox catalysis to prepare novel chiral alpha-aryl phosphate compound.
Detailed Description
The invention will be further illustrated with reference to specific examples, which are not intended to limit the scope of the invention.
Example 1
the photosensitizer 4CzIPN (0.002 mmol,0.0016 g), nickel catalyst NiBr, was added sequentially to a dry Schlenk tube in a glove box under nitrogen atmosphere 2 DME ethylene glycol dimethyl ether Nickel bromide (0.02 mmol,0.0062 g), ligand L1 (0.024 mmol,0.0123 g), cesium carbonate (0.3 mmol,0.0970 g), reducing agent HEH 2, 6-dimethylDiethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid (0.4 mmol,0.1010 g), DMA/1, 4-dioxane (v/v=1/4, 4 ml) was added via syringe, then Schlenk tube was removed from the glove box and the reaction mixture was stirred at room temperature for 30-60 min. Thereafter, the compound was added by a microinjector under nitrogen atmosphere
(0.4 mmol,0.1336 g) and aryl iodides
(0.2 mmol,0.0544 g). After the addition, the Schlenk tube was closed again, the reaction mixture was stirred and irradiated with blue light (λ=450-455 nm) for 8-12 hours, and at the same time, the temperature was controlled to around 15-30 ℃ by a fan and an air conditioner. After completion, the mixture was diluted with ethyl acetate and quenched with water. The aqueous solution was extracted 3 times with ethyl acetate. The combined organic layers were treated with anhydrous Na 2 SO 4 Dried, filtered through celite and concentrated in vacuo. Separating by column chromatography to obtain 0.0658g product
The yield was 82% and the ee value was 93%.
1 H NMR(400MHz,CDCl 3 )δ7.61(d,J＝7.9Hz,2H),7.45(d,J＝8.4Hz,2H),7.27(t,J＝7.6Hz,2H),7.19(t,J＝7.6Hz,1H),7.07(d,J＝7.4Hz,2H),4.09-3.98(m,2H),3.95-3.87(m,1H),3.83-3.73(m,1H),3.07(ddd,J＝22.7,11.1,3.5Hz,1H),2.64-2.57(m,1H),2.50-2.37(m,2H),2.34-2.27(m,1H),1.27(t,J＝7.1Hz,3H),1.11(t,J＝7.0Hz,3H).
13 C NMR(151MHz,CDCl 3 )δ140.5,140.3(d,J＝7.0Hz),129.7(d,J＝6.6Hz),129.4(qd,J＝32.4,3.2Hz),128.4(d,J＝2.7Hz),124.1(q,J＝272.3Hz),126.1,125.4-125.3(m),62.5(d,J＝7.1Hz),62.0(d,J＝7.2Hz),43.6(d,J＝137.5Hz),33.2(d,J＝15.5Hz),30.9(d,J＝3.2Hz),16.3(d,J＝6.0Hz),16.2(d,J＝5.6Hz).
31 P NMR(162MHz,CDCl 3 )δ27.47.
HRMS:m/z(ESI)calculated[M+H] + :401.1488,found:401.1489.
Example 2
the photosensitizer 4CzIPN (0.002 mmol,0.0016 g), nickel catalyst NiBr, was added sequentially to a dry Schlenk tube in a glove box under nitrogen atmosphere 2 DME ethylene glycol dimethyl ether nickel bromide (0.02 mmol,0.0062 g), ligand L1 (0.024 mmol,0.0123 g), cesium carbonate (0.3 mmol,0.0970 g), reducing agent HEH 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester (0.4 mmol,0.1010 g), DMA/1, 4-dioxane (v/v=1/4, 4 mL) was added via syringe, then Schlenk tube was removed from the glove box and the reaction mixture stirred at room temperature for 30-60 min. Thereafter, the compound was added by a microinjector under nitrogen atmosphere
(0.4 mmol,0.1448 g) and aryl iodides
(0.2 mmol,0.0464 g). After the addition, the Schlenk tube was closed again, the reaction mixture was stirred and irradiated with blue light (λ=450-455 nm) for 8-12 hours, and at the same time, the temperature was controlled to around 15-30 ℃ by a fan and an air conditioner. After completion, the mixture was diluted with ethyl acetate and quenched with water. The aqueous solution was extracted 3 times with ethyl acetate. The combined organic layers were treated with anhydrous Na 2 SO 4 Dried, filtered through celite and concentrated in vacuo. Separating by column chromatography to obtain 0.0356g of product
The yield was 46% and the ee value 96%.
1 H NMR(600MHz,CDCl 3 )δ10.0(s,1H),7.87(d,J＝7.9Hz,2H),7.51(dd,J＝8.2,2.2Hz,2H),7.27(t,J＝7.5Hz,2H),7.19(t,J＝7.4Hz,1H),7.07(d,J＝7.1Hz,2H)4.69-4.61(m,1H),4.47-4.41(m,1H),3.03(ddd,J＝22.9,11.2,3.3Hz,1H),,2.62-2.57(m,1H),2.48-2.38(m,2H),2.35-2.29(m,1H),1.26(dd,J＝8.7,6.2Hz,6H),1.21(d,J＝6.1Hz,3H),0.91(d,J＝6.2Hz,3H).
13 C NMR(151MHz,CDCl 3 )δ191.9,143.9(d,J＝6.8Hz),140.6,135.3(d,J＝3.1Hz),130.2(d,J＝6.6Hz),129.8(d,J＝2.6Hz),128.4,126.1,71.1(d,J＝7.2Hz),70.5(d,J＝7.5Hz),44.8(d,J＝138.5Hz),33.4(d,J＝15.6Hz),31.1(d,J＝3.3Hz),24.1(d,J＝3.3Hz),23.9(d,J＝7.5Hz),23.9(d,J＝1.24Hz),23.3(d,J＝5.4Hz).
31 P NMR(243MHz,CDCl 3 )δ25.35.
HRMS:m/z(ESI)calculated[M+Na] + :411.1696,found:411.1701.
Example 3
the photosensitizer 4CzIPN (0.002 mmol,0.0016 g), nickel catalyst NiBr, was added sequentially to a dry Schlenk tube in a glove box under nitrogen atmosphere 2 DME ethylene glycol dimethyl ether nickel bromide (0.02 mmol,0.0062 g), ligand L1 (0.024 mmol,0.0123 g), cesium carbonate (0.3 mmol,0.0970 g), reducing agent HEH 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester (0.4 mmol,0.1010 g), DMA/1, 4-dioxane (v/v=1/4, 4 mL) was added via syringe, then Schlenk tube was removed from the glove box and the reaction mixture stirred at room temperature for 30-60 min. Thereafter, the compound was added by a microinjector under nitrogen atmosphere
(0.4 mmol,0.1448 g) and aryl iodides
(0.2 mmol,0.0520 g). After the addition, the Schlenk tube was closed again, the reaction mixture was stirred and irradiated with blue light (λ=450-455 nm) for 8-12 hours, and at the same time, the temperature was controlled to around 15-30 ℃ by a fan and an air conditioner. After completion, the mixture was diluted with ethyl acetateRelease and quench with water. The aqueous solution was extracted 3 times with ethyl acetate. The combined organic layers were treated with anhydrous Na 2 SO 4 Dried, filtered through celite and concentrated in vacuo. Separating by column chromatography to obtain 0.0283g product
The yield was 34% and the ee value was 93%.
1 H NMR(400MHz,CDCl 3 )δ7.33(d,J＝8.2Hz,2H),7.29-7.22(m,4H),7.20-7.14(m,1H),7.11(d,J＝7.1Hz,2H),4.65-4.57(m,1H),4.39-4.31(m,1H),2.90(ddd,J＝22.3,10.9,3.6Hz,1H),2.65-2.58(m,1H),2.47-2.24(m,3H),1.31(s,9H),1.25(t,J＝5.9Hz,6H),1.19(d,J＝6.2Hz,3H),0.79(d,J＝6.2Hz,3H).
13 C NMR(101MHz,CDCl 3 )δ149.9(d,J＝3.5Hz),141.4,133.0(d,J＝6.8Hz),129.1(d,J＝6.8Hz),128.5,128.3,125.9,125.3(d,J＝2.6Hz),71.0(d,J＝7.3Hz),69.9(d,J＝7.6Hz),43.9(d,J＝139.2Hz),34.4,33.5(d,J＝15.7Hz),31.4(d,J＝2.7Hz),31.4,24.3(d,J＝2.9Hz),24.0(d,J＝7.2Hz),24.0,23.0(d,J＝5.6Hz).
31 P NMR(162MHz,Chloroform-d)δ27.51.
HRMS:m/z(ESI)calculated[M+H] + :417.2553,found:417.2579.
Example 4
the photosensitizer 4CzIPN (0.002 mmol,0.0016 g), nickel catalyst NiBr, was added sequentially to a dry Schlenk tube in a glove box under nitrogen atmosphere 2 DME ethylene glycol dimethyl ether nickel bromide (0.02 mmol,0.0062 g), ligand L1 (0.024 mmol,0.0123 g), cesium carbonate (0.3 mmol,0.0970 g), reducing agent HEH 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester (0.4 mmol,0.1010 g), DMA/1, 4-dioxane (v/v=1/4, 4 mL) was added via syringe, then Schlenk tube was removed from the glove box and the reaction mixture stirred at room temperature for 30-60 min. Thereafter, under a nitrogen atmosphere, usingMicroinjector addition of compounds
(0.4 mmol,0.1448 g) and aryl iodides
(0.2 mmol,0.0794 g). After the addition, the Schlenk tube was closed again, the reaction mixture was stirred and irradiated with blue light (λ=450-455 nm) for 8-12 hours, and at the same time, the temperature was controlled to around 15-30 ℃ by a fan and an air conditioner. After completion, the mixture was diluted with ethyl acetate and quenched with water. The aqueous solution was extracted 3 times with ethyl acetate. The combined organic layers were treated with anhydrous Na 2 SO 4 Dried, filtered through celite and concentrated in vacuo. Separating by column chromatography to obtain 0.0548g product
The yield was 50% and the ee value was 90%.
1 H NMR(600MHz,CDCl 3 )δ7.93(d,J＝8.6Hz,1H),7.75(d,J＝8.4Hz,2H),7.54(d,J＝3.7Hz,1H),7.50(s,1H),7.27-7.20(m,5H),7.16(t,J＝7.3Hz,1H),7.06(d,J＝7.0Hz,2H),6.63(d,J＝3.6Hz,1H),4.62-4.57(m,1H),4.30-4.22(m,1H),2.97(ddd,J＝22.8,11.4,3.2Hz,1H),2.58-2.53(m,1H),2.41-2.37(m,2H),2.33(s,3H),2.30-2.24(m,1H),1.24(dd,J＝6.2,4.5Hz,6H),1.14(d,J＝6.2Hz,3H),0.62(d,J＝6.2Hz,3H).
13 C NMR(151MHz,CDCl 3 )δ144.8,141.1,135.2,134.1(d,J＝2.6Hz),131.3(d,J＝6.5Hz),131.0(d,J＝2.6Hz),129.8,128.8(d,J＝24.2Hz),126.8,126.7,126.3(d,J＝6.5Hz),125.9,122.1(d,J＝7.3Hz),113.4(d,J＝2.2Hz),109.2,70.9(d,J＝7.2Hz),70.0(d,J＝7.6Hz),44.1(d,J＝139.5Hz),33.4(d,J＝15.7Hz),31.6(d,J＝2.7Hz),24.2(d,J＝2.9Hz),24.0(d,J＝10.6Hz),24.0,23.0(d,J＝5.5Hz),21.5.
31 P NMR(243MHz,CDCl 3 )δ27.11.
HRMS:m/z(ESI)calculated[M+Na] + :576.1944,found:576.1932.
Example 5
the photosensitizer 4CzIPN (0.002 mmol,0.0016 g), nickel catalyst NiBr, was added sequentially to a dry Schlenk tube in a glove box under nitrogen atmosphere 2 DME ethylene glycol dimethyl ether nickel bromide (0.02 mmol,0.0062 g), ligand L1 (0.024 mmol,0.0123 g), cesium carbonate (0.3 mmol,0.0970 g), reducing agent HEH 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester (0.4 mmol,0.1010 g), DMA/1, 4-dioxane (v/v=1/4, 4 mL) was added via syringe, then Schlenk tube was removed from the glove box and the reaction mixture stirred at room temperature for 30-60 min. Thereafter, the compound was added by a microinjector under nitrogen atmosphere
(0.4 mmol,0.1448 g) and aryl iodides
(0.2 mmol,0.0420 g). After the addition, the Schlenk tube was closed again, the reaction mixture was stirred and irradiated with blue light (λ=450-455 nm) for 8-12 hours, and at the same time, the temperature was controlled to around 15-30 ℃ by a fan and an air conditioner. After completion, the mixture was diluted with ethyl acetate and quenched with water. The aqueous solution was extracted 3 times with ethyl acetate. The combined organic layers were treated with anhydrous Na 2 SO 4 Dried, filtered through celite and concentrated in vacuo. Separating by column chromatography to obtain 0.0431g product
The yield was 59% and the ee value was 92%.
1 H NMR(600MHz,CDCl 3 )δ7.30(dd,J＝5.0,3.0Hz,1H),7.26(t,J＝7.5Hz,2H),7.19–7.14(m,2H),7.12–7.09(m,3H),4.64-4.58(m,1H),4.46-4.40(m,1H),3.09(ddd,J＝22.2,11.4,3.5Hz,1H),2.66-2.61(m,1H),2.45-2.40(m,1H),2.39-2.32(m,1H),2.24-2.16(m,1H),1.25(dd,J＝6.2,4.1Hz,6H),1.22(d,J＝6.2Hz,3H),0.93(d,J＝6.2Hz,3H).
13 C NMR(151MHz,CDCl 3 )δ141.1,136.3(d,J＝7.1Hz),128.5,128.3(d,J＝4.4Hz),128.3,125.9,125.3,123.0(d,J＝10.0Hz),71.0(d,J＝7.2Hz),70.0(d,J＝7.6Hz),39.6(d,J＝142.0Hz),33.4(d,J＝15.6Hz),31.6(d,J＝2.7Hz),24.2(d,J＝3.0Hz),23.9(d,J＝7.6Hz),23.9(d,J＝1.5Hz),23.2(d,J＝5.5Hz).
31 P NMR(243MHz,CDCl 3 )δ26.39.
HRMS:m/z(ESI)calculated[M+Na] + :389.1311,found:389.1313.
Example 6
the photosensitizer 4CzIPN (0.002 mmol,0.0016 g), nickel catalyst NiBr, was added sequentially to a dry Schlenk tube in a glove box under nitrogen atmosphere 2 DME ethylene glycol dimethyl ether nickel bromide (0.02 mmol,0.0062 g), ligand L1 (0.024 mmol,0.0123 g), cesium carbonate (0.3 mmol,0.0970 g), reducing agent HEH 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester (0.4 mmol,0.1010 g), DMA/1, 4-dioxane (v/v=1/4, 4 mL) was added via syringe, then Schlenk tube was removed from the glove box and the reaction mixture stirred at room temperature for 30-60 min. Thereafter, the compound was added by a microinjector under nitrogen atmosphere
(0.4 mmol,0.1680 g) and aryl iodide +.>
(0.2 mmol,0.0544 g). After the addition, the Schlenk tube was closed again, the reaction mixture was stirred and irradiated with blue light (λ=450-455 nm) for 8-12 hours, and at the same time, the temperature was controlled to around 15-30 ℃ by a fan and an air conditioner. After completion, the mixture was diluted with ethyl acetate and quenched with water. The aqueous solution was extracted 3 times with ethyl acetate. The combined organic layers were treated with anhydrous Na 2 SO 4 The drying is carried out,filtered through celite and concentrated in vacuo. Separating by column chromatography to obtain 0.0669g of product
The yield was 69% and the ee value 96%.
1 H NMR(600MHz,CDCl 3 )δ8.01(dd,J＝8.3,1.4Hz,2H),7.59-7.54(m,3H),7.48-7.42(m,4H),4.72-4.42(m,1H),4.47-4.42(m,1H),4.28(t,J＝6.4Hz,2H),3.06(ddd,J＝23.0,11.5,3.9Hz,1H),2.32-2.28(m,1H),2.15-2.06(m,1H),1.70-1.65(m,2H),1.27(d,J＝6.4Hz,6H),1.23(d,J＝6.2Hz,3H),0.91(d,J＝6.2Hz,3H).
13 C NMR(151MHz,CDCl 3 )δ166.4,140.6(d,J＝6.9Hz),132.9,129.7(d,J＝6.8Hz),129.5,129.4(qd,J＝31.7,3.0Hz),128.3,125.4-125.3(m),124.1(q,J＝271.8Hz),71.2(d,J＝7.2Hz),70.5(d,J＝7.5Hz),63.98,44.8(d,J＝139.8Hz),26.8(d,J＝15.5Hz),26.4(d,J＝3.4Hz),24.1(d,J＝3.3Hz),23.9,23.9(d,J＝2.8Hz),23.2(d,J＝5.5Hz).
31 P NMR(243MHz,CDCl 3 )δ25.36.
HRMS:m/z(ESI)calculated[M+H] + :487.1856,found:487.1849.
Example 7
the photosensitizer 4CzIPN (0.002 mmol,0.0016 g), nickel catalyst NiBr, was added sequentially to a dry Schlenk tube in a glove box under nitrogen atmosphere 2 DME ethylene glycol dimethyl ether nickel bromide (0.02 mmol,0.0062 g), ligand L1 (0.024 mmol,0.0123 g), cesium carbonate (0.3 mmol,0.0970 g), reducing agent HEH 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester (0.4 mmol,0.1010 g), DMA/1, 4-dioxane (v/v=1/4, 4 mL) was added via syringe, then Schlenk tube was removed from the glove box and the reaction mixture stirred at room temperature for 30-60 min. Thereafter, the compound was added by a microinjector under nitrogen atmosphere
(0.4 mmol,0.1344 g) and aryl iodide
(0.2 mmol,0.0544 g). After the addition, the Schlenk tube was closed again, the reaction mixture was stirred and irradiated with blue light (λ=450-455 nm) for 8-12 hours, and at the same time, the temperature was controlled to around 15-30 ℃ by a fan and an air conditioner. After completion, the mixture was diluted with ethyl acetate and quenched with water. The aqueous solution was extracted 3 times with ethyl acetate. The combined organic layers were treated with anhydrous Na 2 SO 4 Dried, filtered through celite and concentrated in vacuo. Separating by column chromatography to obtain 0.0562g of product
The yield was 70% and the ee value was 81%.
1 H NMR(600MHz,CDCl 3 )δ7.86-7.83(m,2H),7.52-7.46(m,3H),7.37-7.34(m,4H),7.29-7.25(m,3H),7.19-7.15(m,2H),3.46-3.42(m,1H),2.11-2.05(m,1H),1.80-1.73(m,1H),1.17-1.10(m,1H),1.06-1.00(m,1H),0.72(td,J＝7.4,2.4Hz,3H).
13 C NMR(151MHz,CDCl 3 )δ140.4(d,J＝5.2Hz),131.9(d,J＝60.4Hz),131.9(d,J＝2.7Hz),131.4(d,J＝2.8Hz),131.3(d,J＝57.4Hz),131.2(d,J＝8.3Hz),130.7(d,J＝8.6Hz),130.0(d,J＝5.6Hz),129.0(qd,J＝31.7,3.0Hz),128.8(d,J＝11.5Hz),128.1(d,J＝11.6Hz),125.1-125.0(m),129.0(q,J＝271.8Hz),46.6(d,J＝66.5Hz),31.0,20.8(d,J＝12.9Hz),13.5.
31 P NMR(243MHz,CDCl 3 )δ32.47.
HRMS:m/z(ESI)calculated[M+Na] + :425.1253,found:425.1240.
Example 8
in a glove box under nitrogen atmosphere, to dry SchlenkPhotosensitizer 4CzIPN (0.002 mmol,0.0016 g), nickel catalyst NiBr, was added sequentially to the tube 2 DME ethylene glycol dimethyl ether nickel bromide (0.02 mmol,0.0062 g), ligand L1 (0.024 mmol,0.0123 g), cesium carbonate (0.3 mmol,0.0970 g), reducing agent HEH 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester (0.4 mmol,0.1010 g), DMA/1, 4-dioxane (v/v=1/4, 4 mL) was added via syringe, then Schlenk tube was removed from the glove box and the reaction mixture stirred at room temperature for 30-60 min. Thereafter, the compound was added by a microinjector under nitrogen atmosphere
(0.4 mmol,0.1344 g) and aryl iodide
(0.2 mmol,0.0544 g). After the addition, the Schlenk tube was closed again, the reaction mixture was stirred and irradiated with blue light (λ=450-455 nm) for 8-12 hours, and at the same time, the temperature was controlled to around 15-30 ℃ by a fan and an air conditioner. After completion, the mixture was diluted with ethyl acetate and quenched with water. The aqueous solution was extracted 3 times with ethyl acetate. The combined organic layers were treated with anhydrous Na 2 SO 4 Dried, filtered through celite and concentrated in vacuo. Column chromatography gave 0.0457g of product
The yield was 55%, the ee value was 81%, and the ee value after recrystallization was 95%.
1 H NMR(600MHz,CDCl 3 )δ7.76(dd,J＝10.6,7.9Hz,2H),7.34-7.28(m,4H),7.23(dd,J＝8.7,2.1Hz,2H),7.07-7.02(m,4H),3.60-3.55(m,1H),2.42(s,3H),2.29(s,3H),1.54(dd,J＝15.9,7.3Hz,3H).
13 C NMR(151MHz,CDCl 3 )δ148.0,142.2(d,J＝2.8Hz),141.8(d,J＝2.8Hz),137.0(d,J＝5.6Hz),131.3(d,J＝8.8Hz),130.9(d,J＝8.9Hz),130.4(d,J＝5.2Hz),129.4(d,J＝11.6Hz),128.8(d,J＝12.1Hz),128.3(q,J＝33.2Hz),120.6-120.6(m),127.8,120.4(q,J＝258.2Hz),40.4(d,J＝67.1Hz),31.3,21.5(d,J＝19.9Hz),15.4(d,J＝2.7Hz).
31 P NMR(243MHz,CDCl 3 )δ33.79.
HRMS:m/z(ESI)calculated[M+Na] + :441.1202,found:441.1189.
Example 9
the compound prepared in example 7 was added sequentially to a dry 10mL Schlenk tube in a glove box filled with nitrogen
(0.1 mmol), triethylamine (2 mmol) and degassed toluene (1 mL). Trichlorosilane (1 mmol) was added dropwise to the reaction tube using a syringe, the Schlenk tube was closed, and the mixture was taken out of the glove box. The reaction mixture was then stirred in an oil bath at 110-130 ℃ for 20-28 hours. After cooling the reaction tube to room temperature, it was again transferred to a glove box, filtered through a pad of celite, washed with n-hexane, and the solvent was removed in vacuo. Yield 0.0277g of product +.>
The yield was 72%.
1 H NMR(600MHz,CDCl 3 )δ7.69-7.66(m,2H),7.45-7.42(m,5H),7.24-7.19(m,3H),7.14-7.09(m,4H),3.60-3.56(m,1H),1.93-1.85(m,1H),1.77-1.70(m,1H),1.23-1.19(m,1H),1.16-1.11(m,1H),0.79(t,J＝7.3Hz,3H).
13 C NMR(151MHz,CDCl 3 )δ144.8(d,J＝6.8Hz),134.6(d,J＝3.8Hz),134.4(d,J＝6.1Hz),133.8(d,J＝19.3Hz),133.2(d,J＝17.7Hz),129.9,129.4(d,J＝7.5Hz),129.1,128.8(d,J＝7.8Hz),128.4(qd,J＝31.7,3.0Hz),128.1(d,J＝7.3Hz),125.2-125.1(m),124.2(q,J＝271.8Hz),44.7(d,J＝8.3Hz),34.7(d,J＝17.7Hz),20.9(d,J＝11.0Hz),13.7. 31 P NMR(243MHz,CDCl 3 )δ0.79.HRMS:m/z(ESI)calculated[M+H] + :387.1484,found:387.1446.
Example 10
the compound prepared in example 8 was added sequentially to a dry 10mL Schlenk tube in a glove box filled with nitrogen
(0.1 mmol), triethylamine (2 mmol) and degassed toluene (1 mL). Trichlorosilane (1 mmol) was added dropwise to the reaction tube using a syringe, the Schlenk tube was closed, and the mixture was taken out of the glove box. The reaction mixture was then stirred in an oil bath at 110-130 ℃ for 20-28 hours. After cooling the reaction tube to room temperature, it was again transferred to a glove box, filtered through a pad of celite, washed with n-hexane, and the solvent was removed in vacuo. Yield 0.0365g of product +.>
The yield was 91%.
1 H NMR(600MHz,CDCl 3 )δ7.43(t,J＝7.6Hz,2H),7.15(d,J＝7.5Hz,2H),7.05(d,J＝8.2Hz,2H),6.94(d,J＝8.2Hz,2H),6.91-6.86(m,4H),3.48-3.43(m,1H),2.30(s,3H),2.16(s,3H),1.32(dd,J＝14.7,7.1Hz,3H).
13 C NMR(151MHz,CDCl 3 )δ147.4,142.2,139.5,138.6,133.9(d,J＝20.2Hz),133.0(d,J＝17.9Hz),129.6(d,J＝7.3Hz),129.4(d,J＝7.3Hz),128.8(d,J＝7.1Hz),120.7,129.5(q,J＝256.7Hz),120.7-120.7(m),38.5(d,J＝11.2Hz),29.7,21.3(d,J＝27.1Hz),19.4(d,J＝19.8Hz). 31 P NMR(243MHz,CDCl 3 )δ1.77.HRMS:m/z(ESI)calculated[M+H] + :403.1433,found:403.1423.
Example 11
imidazole (1.2 mmol), triphenylphosphine (1.2 mmol) and dichloromethane (6 mL) were added sequentially to a 25mL round bottom flask at 0deg.C for 10 minBromine water (1.2 mmol) was slowly added dropwise over clock and the mixture was stirred for 10 minutes. Thereafter, the compound is added
(0.6 mmol) and the resulting mixture was warmed to 40-60 ℃ and stirred overnight. Next, water was added to the reaction mixture. The organic layer was then separated and the aqueous layer extracted twice with dichloromethane. Concentrating the combined organic layers, and separating by column chromatography to obtain 0.1990g of product ∈>
The yield was 75%,92% ee.
1 H NMR(600MHz,CDCl 3 )δ7.58(d,J＝8.0Hz,2H),7.45(d,J＝6.0Hz,2H),4.73-4.67(m,1H),4.51-4.44(m,1H),3.38-3.31(m,2H),3.02(ddd,J＝23.0,11.4,4.1Hz,1H),2.33-2.25(m,1H),2.14-2.06(m,1H),1.79-1.70(m,2H),1.31(dd,J＝6.2,2.6Hz,6H),1.25(d,J＝6.2Hz,3H),0.96(d,J＝6.2Hz,3H).
13 C NMR(151MHz,CDCl 3 )δ140.3(d,J＝7.0Hz),129.6(d,J＝6.7Hz),129.6(qd,J＝33.2,3.0Hz),125.5-125.4(m),124.0(q,J＝271.8Hz),71.6(d,J＝7.3Hz),70.9(d,J＝7.4Hz),44.5(d,J＝140.2Hz),32.7,30.6(d,J＝15.6Hz),28.3(d,J＝3.3Hz),24.1(d,J＝3.3Hz),24.0,23.9(d,J＝2.2Hz),23.3(d,J＝5.5Hz). 31 P NMR(243MHz,CDCl 3 )δ24.90.HRMS:m/z(ESI)calculated[M+Na] + :467.0569,found:467.0579.
The compound was added to a dry 10mL Schlenk tube
(0.1 mmol), compound
(0.2mmol)、K 2 CO 3 (0.2 mmol), naI (0.1 mmol) and acetonitrile (1 mL) and refluxed overnight at 80-90 ℃. Cooling the reaction mixture to room temperature, filtering, concentrating under reduced pressure, and separating by column chromatography (ethyl acetate: petroleum ether=1:2) to obtain 0.0202g of product->
The yield was 41%.
1 H NMR(600MHz,CDCl 3 )δ7.56(d,J＝8.0Hz,2H),7.44(d,J＝8.3Hz,2H),4.69-4.64(m,1H),4.48-4.42(m,1H),4.13(q,J＝7.1Hz,2H),3.29(q,J＝7.0Hz,1H),3.01(ddd,J＝22.8,11.5,3.8Hz,1H),2.50-2.39(m,2H),2.22(s,3H),2.12-2.07(m,1H),1.98-1.92(m,1H),1.35-1.31(m,2H),1.28(dd,J＝6.2,3.5Hz,6H),1.25-1.22(m,9H),0.93(d,J＝6.2Hz,3H).
13 C NMR(151MHz,CDCl 3 )δ173.2,141.0(d,J＝6.5Hz),129.7(d,J＝6.7Hz),129.2(qd,J＝33.2,3.0Hz),125.3-125.2(m),124.1(q,J＝271.8Hz),71.0(d,J＝7.3Hz),70.4(d,J＝7.4Hz),61.3,60.1,53.3,45.1(d,J＝139.2Hz),37.9,27.4(d,J＝3.5Hz),25.9(d,J＝15.3Hz),24.2(d,J＝3.3Hz),23.97,23.9(d,J＝2.8Hz),23.2(d,J＝5.5Hz),14.6(d,J＝87.8Hz). 31 P NMR(243MHz,CDCl 3 )δ25.87.HRMS:m/z(ESI)calculated[M+Na] + :518.2254,found:518.2253.
In a 10mL reaction tube, the compound was reacted with
(0.04 mmol) was dissolved in methanol/water (5:1, 0.1M), lithium hydroxide (0.16 mmol) was added, and the reaction mixture was stirred at room temperature overnight. Then, 2N HCl was slowly added to the reaction mixture and concentrated in vacuo to give the desired acidified product, which was used without further purification. Then, the compound->
(0.044 mmol) was added to the product of the previous step and THF/DMF (v/v=1/9, 1 mL) was added followed by BOP= [ O- (benzotriazol-1-yl) -N, N, N ', N' -tetramethylurea tetrafluoroborate](0.08 mmol) and N, N-diisopropylethylamine (0.24 mmol). After completion of the reaction, water was added to the reaction mixture, extracted 3 times with ethyl acetate, and concentrated in vacuo. Flash chromatography on silica gel, separation by column chromatography (ethyl acetate: petroleum ether)=1:1), giving pure 0.0158g of product +.>
The yield thereof was found to be 63%.
1 H NMR(600MHz,CDCl 3 )δ7.58(d,J＝7.9Hz,2H),7.50(d,J＝8.1Hz,1H),7.44(d,J＝6.0Hz,2H),7.25-7.19(m,3H),7.10(d,J＝6.6Hz,2H),4.80-4.76(m,1H),4.69-4.64(m,1H),4.48-4.43(m,1H),3.71(s,3H),3.17(dd,J＝14.0,5.6Hz,1H),3.06-2.93(m,3H),2.32-2.26(m,2H),2.09-1.98(m,1H),1.89(s,3H),1.86-1.84(m,1H),1.34-1.30(m,2H),1.28(dd,J＝6.2,3.7Hz,6H),1.23(d,J＝6.2Hz,3H),1.05(d,J＝7.0Hz,3H),0.94(d,J＝6.1Hz,3H).
13 C NMR(151MHz,CDCl 3 )δ174.0,172.1,136.1,129.7(d,J＝6.7Hz),129.3(qd,J＝33.2,3.0Hz),128.8(d,J＝92.4Hz),127.0,125.3-125.2(m),124.1(q,J＝270.3Hz),71.1(d,J＝7.2Hz),70.4(d,J＝7.2Hz),63.3,54.6,52.7,52.2,45.2(d,J＝139.3Hz),37.6(d,J＝60.8Hz),29.7,27.4(d,J＝3.4Hz),26.0(d,J＝14.4Hz),24.2(d,J＝3.3Hz),24.0(d,J＝7.6Hz),24.0,23.3(d,J＝5.5Hz),10.4. 31 P NMR(243MHz,CDCl 3 )δ25.65.HRMS:m/z(ESI)calculated[M+Na] + :651.2781,found:651.2749.
Those skilled in the art will understand that the skilled person can implement the modification in combination with the prior art and the above embodiments, and this will not be repeated here. Such modifications do not affect the essence of the present invention, and are not described herein.
The preferred embodiments of the present invention have been described above. It is to be understood that the invention is not limited to the specific embodiments described above, wherein devices and structures not described in detail are to be understood as being implemented in a manner common in the art; any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or modifications to equivalent embodiments without departing from the scope of the technical solution of the present invention, using the methods and technical contents disclosed above, without affecting the essential content of the present invention. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (3)
1. A method for synthesizing chiral alpha-aryl phosphate, which is characterized by comprising the following steps:
(1) Under the inert gas atmosphere, adding a photosensitizer, a nickel catalyst, a chiral ligand, alkali and a reducing agent into an organic solvent for reaction;
(2) Adding alpha-bromophosphate and aryl halide into the reaction liquid prepared in the step (1) in an inert gas atmosphere to react to obtain chiral alpha-aryl phosphate shown in a formula (II) or a formula (IV), wherein the structural formula of the alpha-bromophosphate is shown in a formula (I) or a formula (III);
wherein R is 1 、R 2 Is alkyl or aryl, ar' is aryl;
the photosensitizer is 2,4,5, 6-tetra (9-carbazolyl) -m-phthalonitrile;
the nickel catalyst is ethylene glycol dimethyl ether nickel bromide;
the chiral ligand is a ligand shown as a formula (L1);
the base is cesium carbonate;
the reducing agent is diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid;
the organic solvent is a mixture of 1, 4-dioxane and N, N' -dimethylacetamide;
the reaction temperature of the reaction in the step (1) is 15-30 ℃ and the reaction time is 30-60 min;
the reaction in the step (2) is carried out for 8-12 h under the conditions of illumination of a 30W blue light lamp and 15-30 ℃.
2. The method of claim 1, wherein the α -bromo phosphate is used in an amount of 100 to 600% molar equivalents of the aryl halide;
the amount of the base is 50 to 500% molar equivalent of the aryl halide;
the amount of the reducing agent is 100-500% molar equivalent of the aryl halide;
the nickel catalyst is used in an amount of 1 to 200% molar equivalent of the aryl halide;
the dosage of the photosensitizer is 0.5-200% of the molar equivalent of aryl halide;
the chiral ligand is used in an amount of 1 to 200% molar equivalents of the aryl halide.
3. The method of claim 2, wherein the α -bromo phosphate is used in an amount of 200% molar equivalents of aryl halide;
the base is used in an amount of 150% molar equivalents of the aryl halide;
the reducing agent is used in an amount of 200% molar equivalents of the aryl halide;
the nickel catalyst is used in an amount of 10% molar equivalents of aryl halide;
the photosensitizer is used in an amount of 1% molar equivalent of the aryl halide;
the chiral ligand is used in an amount of 12% molar equivalents of the aryl halide.
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