Preparation method of organic germanium compound induced by visible light
Through visible light-induced germanylation synthesis method, functional group compatibility problems in traditional organic germany compound synthesis are solved, efficient and environmentally friendly germanylation synthesis is achieved, and the application potential of functional materials and drug molecules is expanded.
Patent Information
- Application Number
- CN202510397917.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-01
- Publication Date
- 2025-07-04
AI Technical Summary
Traditional organic germanium compound synthesis methods have functional group compatibility problems, resulting in low synthesis efficiency and limited molecular design diversity, making it difficult to meet the needs of functional materials and drug molecules.
Using visible light induction method, using germane hydride and high-valent iodine reagent as starting materials, under the catalysis of the photocatalyst 9,10-phenanthrenequinone, series of alkynyl, alkenyl, nitrile, and phenylgermane are synthesized through the direct hydrogen atom transfer process, avoiding the transition metal catalysis and strong alkalinity problems in the traditional methods.
The germanyl synthesis synthesis with environmentally friendly and mild conditions has been achieved, the scope of application of substrates has been expanded, and the post-germany modification methods of drug molecular derivatives have potential biological activities and pharmacological effects.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the field of organic synthesis, relates to the preparation of organogermanium compounds, and specifically relates to a method for preparing organogermanium compounds induced by visible light. Background Art
[0002] The research on the synthesis methods of organogermanium compounds is of great significance for accelerating the discovery of functional germanium-containing molecules, and also shows great potential in the development of functional materials and candidate drug molecules. Germanium (Ge) endows such compounds with unique physical and chemical properties, such as stability, hydrophobicity and low toxicity, making them ideal candidate structures in the fields of materials science and medicinal chemistry. The progress of modern chemical synthesis technology has further highlighted the versatility of organogermanium compounds as orthogonal coupling reagents in bonding strategies, opening up new ways for their applications. Therefore, the continuous innovation of organogermanium compound synthesis methods has always been the focus of academic attention. However, the traditional synthesis routes of organogermanium compounds mainly rely on the reactivity of organometallic compounds, such as the substitution reaction of Grignard reagents with germanium electrophiles (such as R3GeCl), or the reaction of germanium metal species with other electrophiles. However, the strong basicity and nucleophilicity of organometallic reagents may lead to functional group compatibility problems and reduce the regioselectivity of chemical transformation, thus limiting the synthesis efficiency and the diversity of molecular design. Therefore, the development of new synthesis strategies to overcome the challenges of traditional methodologies is crucial for promoting the development and application of organogermanium chemistry. Summary of the Invention
[0003] The purpose of the present invention is to overcome the deficiencies of the prior art and explore a visible-light-induced germanium alkylation synthesis method. The present invention uses germane hydride and hypervalent iodine reagent as starting materials, and synthesizes a series of alkynyl, alkenyl, nitrile, phenylgermanes under the catalysis of the photocatalyst 9,10-phenanthrenequinone. This method has many advantages such as mild reaction conditions, atom and step economy, metal-free catalysis, green sustainability, etc. More importantly, this method can be applied to the post-germanylation modification of many drug molecule derivatives, showing its great application prospects in the field of pharmaceutical chemistry.
[0004] A method for preparing an organogermanium compound induced by visible light according to the present invention is realized by adopting the following technical solutions:
[0005] A preparation method of a visible light-induced organogermanium compound, and the specific method steps include: dissolving germane hydride and a hypervalent iodine reagent in dimethyl sulfoxide, adding a molar ratio of 1 germane hydride: 2 hypervalent iodine reagent, and then adding a photocatalyst 9,10-phenanthrenequinone to the reaction system. The molar fraction ratio of germane hydride to the photocatalyst 9,10-phenanthrenequinone is 1:5 mol%. Stir the reaction at room temperature. The reaction occurs under irradiation of 430 nm blue light in a nitrogen atmosphere, and the stirring time at room temperature is 12 h. After the reaction is completed, extract, dry, and rotary evaporate to remove the organic solvent, and separate by column chromatography. The stationary phase of the column chromatography is silica gel G, and the mobile phase is a mixed solvent of petroleum ether and ethyl acetate. The target organogermanium compound is obtained after separation.
[0006] Moreover, the reaction equation of the preparation method is as follows:
[0007]
[0008] Moreover, the structural formula of the organogermanium compound wherein R includes any one or more of phenyl or n-butyl; FG includes any one or more of alkynyl, alkenyl, nitrile group or phenyl.
[0009] Moreover, the germane hydride The structural formula is Any one or more of them.
[0010] Moreover, wherein FG includes any one or more of alkynyl, alkenyl, nitrile group or phenyl.
[0011] The beneficial effects of the present invention are:
[0012] The method of the present invention innovatively realizes visible light-driven germyl radical initiation through a direct hydrogen atom transfer process and conducts subsequent germyl functionalization reactions. This method overcomes the limitation that traditional photocatalytic germyl radical chemistry can only perform hydrogermylation, and under the catalysis of the photocatalyst 9,10-phenanthrenequinone, a series of alkynyl, alkenyl, nitrile group, phenylgermanes are successfully synthesized. The reaction has the advantages of environmental friendliness, mild conditions, simple operation, high atom economy, wide substrate scope, etc. Applying this method, post-modification of germylation of drug molecule derivatives can also be realized, providing a convenient means for constructing organogermanium compounds with potential biological activities and pharmacological effects. The invention has great application prospects in the field of pharmaceutical chemistry, opening up a new idea for the design and synthesis of germanium-containing functional molecules. Specific embodiments
[0013] Next, in combination with the embodiments of the present invention, the technical solutions of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
[0014] Example 1
[0015] In a 25 mL Schlenk tube, triphenylgermane (0.1 mmol), hypervalent iodine alkyne reagent (0.2 mmol, 2.0 equivalents), and 9,10-phenanthrenequinone (5 mol%) were dissolved in 1 mL of dimethyl sulfoxide. The reaction mixture was irradiated with a 10 W 430 nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate (3 × 5 mL) and saturated sodium chloride solution (3 × 5 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The resulting residue was purified by silica gel column chromatography using petroleum ether as the eluent to finally obtain the target product.
[0016]
[0017] Purification by flash column chromatography(PE).Colorless oil(32mg,78%yield). 1 H NMR(600MHz,Chloroform-d)δ7.70–7.66(m,6H),7.60–7.57(m,2H),7.45–7.38(m,9H),7.35–7.31(m,3H). 13 C NMR(151MHz,Chloroform-d)δ135.2,134.6,132.2,129.5,128.7,128.4,128.3,123.1,108.1,88.7.HRMS(ESI-TOF)m / z:[M+Na] + calcd forC 26 H 20 NaGe + ,429.0669,found:429.0657.
[0018] Example 2
[0019] In a 25 mL Schlenk tube, tributylgermane hydride (0.1 mmol), hypervalent iodine alkyne reagent (0.2 mmol, 2.0 equiv), and 9,10-phenanthrenequinone (5 mol%) were dissolved in 1 mL of dimethyl sulfoxide. The reaction mixture was irradiated with a 10 W 430 nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate (3 × 5 mL) and saturated sodium chloride solution (3 × 5 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The resulting residue was purified by silica gel column chromatography using cyclohexane as the eluent to finally obtain the target product.
[0020]
[0021] Purification by flash column chromatography(cyclohexane).Colorlessoil(15mg,42%yield). 1 1H NMR(400MHz,Chloroform-d)δ7.48–7.41(m,2H),7.33–7.19(m,3H),1.58–1.43(m,6H),1.43–1.32(m,6H),1.04–0.86(m,15H). 13 13C NMR(101MHz,Chloroform-d)δ131.9,128.1,127.9,123.9,105.8,92.9,27.4,26.1,14.2,13.8.HRMS(ESI-TOF)m / z:[M+Na] + calcd for C 20 H 32 NaGe + ,369.1608,found:369.1605.
[0022] Example 3
[0023] In a 25 mL Schlenk tube, diphenyldigermane (0.1 mmol), hypervalent iodine alkyne reagent (0.2 mmol, 2.0 equiv), and 9,10-phenanthrenequinone (5 mol%) were dissolved in 1 mL of dimethyl sulfoxide. The reaction mixture was irradiated with a 10 W 430 nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate (3 × 5 mL) and saturated sodium chloride solution (3 × 5 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The resulting residue was purified by silica gel column chromatography using cyclohexane as the eluent to finally obtain the target product.
[0024]
[0025] Purification by flash column chromatography(cyclohexane).Colorless oil(19mg,45%yield). 1 H NMR(400MHz,Chloroform-d)δ7.92–7.74(m,4H),7.72–7.53(m,4H),7.49–7.41(m,6H),7.39–7.28(m,6H). 13 C NMR(101MHz,Chloroform-d)δ134.4,133.9,132.3,129.9,128.9,128.6,128.2,122.7,107.1,86.9.HRMS(ESI-TOF)m / z:[M+Na] + calcd for C 28 H 20 NaGe + ,453.0669,found:453.0670.
[0026] Example 4
[0027] In a 25 mL Schlenk tube, triphenylgermane hydride (0.1 mmol), hypervalent iodine alkyne reagent (0.2 mmol, 2.0 equiv), and 9,10-phenanthrenequinone (5 mol%) were dissolved in 1 mL of dimethyl sulfoxide. The reaction mixture was irradiated with a 10 W 430 nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate (3 × 5 mL) and saturated sodium chloride solution (3 × 5 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The resulting residue was purified by silica gel column chromatography using a petroleum ether / ethyl acetate mixed solvent as the eluent to finally obtain the target product.
[0028]
[0029] Purification by flash column chromatography(PE:EA,v / v=20:1).Colorless oil(23mg,35%yield). 11H NMR (600 MHz, Chloroform-d) δ 7.72–7.61 (m, 6H), 7.59–7.52 (m, 4H), 7.48–7.36 (m, 13H), 7.24–7.18 (m, 2H), 7.02 (d, J = 8.6 Hz, 2H), 3.99 (q, J = 7.1 Hz, 1H), 1.65 (d, J = 7.2 Hz, 3H). 13 13C NMR (151 MHz, Chloroform-d) δ 172.1, 159.8 (d, J = 248.7 Hz), 150.8, 141.1 (d, J = 7.5 Hz), 135.4, 135.1, 134.6, 133.4, 131.1 (d, J = 3.9 Hz), 129.6, 128.9 (d, J = 2.9 Hz), 128.5, 128.4, 128.2 (d, J = 13.7 Hz), 127.8, 123.6 (d, J = 3.4 Hz), 121.4, 120.9, 115.4 (d, J = 23.8 Hz), 107.1, 89.1, 45.2, 18.4. 19 19F NMR (565 MHz, Chloroform-d) δ -117.17. HRMS (ESI-TOF) m / z: [[M+Na]] + C 41 H 31 FO2NaGe + , 671.1412, found: 671.1411.
[0030] Example 5
[0031] In a 25 mL Schlenk tube, triphenylgermane hydride (0.1 mmol), hypervalent iodine alkyne reagent (0.2 mmol, 2.0 equiv), and 9,10-phenanthrenequinone (5 mol%) were dissolved in 1 mL of dimethyl sulfoxide. The reaction mixture was irradiated with a 10 W 430 nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate (3 × 5 mL) and saturated sodium chloride solution (3 × 5 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The resulting residue was purified by silica gel column chromatography using a petroleum ether / ethyl acetate mixed solvent as the eluent to finally obtain the target product.
[0032]
[0033] Purification by flash column chromatography(PE:EA,v / v=20:1).Colorless oil(27mg,45%yield). 1 1H NMR(600MHz,Chloroform-d)δ7.73–7.59(m,6H),7.56–7.51(m,2H),7.43–7.36(m,9H),7.31–7.27(m,2H),7.17–7.12(m,2H),6.99–6.96(m,2H),3.93(q,J=7.1Hz,1H),2.47(d,J=7.2Hz,2H),1.90–1.77(m,1H),1.60(d,J=7.1Hz,3H),0.91(d,J=6.6Hz,6H). 13 13C NMR(151MHz,Chloroform-d)δ172.9,151.0,140.9,137.0,135.1,134.6,133.3,129.6(d,J=3.3Hz),128.4,127.2,121.5,120.6,107.3,88.9,45.2(d,J=34.3Hz),30.2,22.4,18.5.HRMS(ESI-TOF)m / z:[M+Na] + calcd for C 39 H 36 O2NaGe + ,633.1819,found:633.1816.
[0034] Example 6
[0035] In a 25 mL Schlenk tube, triphenylgermane hydride(0.1 mmol), hypervalent iodine alkyne reagent(0.2 mmol, 2.0 equivalents), and 9,10-phenanthrenequinone(5 mol%) were dissolved in 1 mL of dimethyl sulfoxide. The reaction mixture was irradiated with a 10 W 430 nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate(3×5 mL) and saturated sodium chloride solution(3×5 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The resulting residue was purified by silica gel column chromatography using a petroleum ether / ethyl acetate mixed solvent as the eluent to finally obtain the target product.
[0036]
[0037] Purification by flash column chromatography(PE:EA,v / v=20:1).Colorless oil(29mg,45%yield). 1 1H NMR(600MHz,Chloroform-d)δ7.80–7.70(m,3H),7.69–7.58(m,6H),7.54–7.49(m,2H),7.50–7.47(m,1H),7.44–7.35(m,9H),7.18–7.11(m,2H),7.01–6.89(m,2H),4.09(q,J=7.1Hz,1H),3.92(s,3H),1.69(d,J=7.1Hz,3H). 13 13C NMR(151MHz,Chloroform-d)δ172.8,157.8,150.9,135.1,134.9,134.6,133.9,133.3,129.5,129.3,129.0,128.4,127.4,126.2,126.1,121.5,120.7,119.2,105.6,88.9,55.4,45.6,18.5.HRMS(ESI-TOF)m / z:[M+Na] + calcd for C 40 H 32 O3NaGe + ,657.1455,found:657.1442.
[0038] Example 7
[0039] In a 25 mL Schlenk tube, triphenylgermane hydride(0.1 mmol), hypervalent iodine alkyne reagent(0.2 mmol, 2.0 equiv), and 9,10-phenanthrenequinone(5 mol%) were dissolved in 1 mL of dimethyl sulfoxide. The reaction mixture was irradiated with a 10 W 430 nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate(3×5 mL) and saturated sodium chloride solution(3×5 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The resulting residue was purified by silica gel column chromatography using a petroleum ether / ethyl acetate mixed solvent as the eluent to finally obtain the target product.
[0040]
[0041] Purification by flash column chromatography (PE: EA, v / v = 20:1). Colorless oil (31 mg, 50% yield). 1 H NMR (600MHz, Chloroform-d) δ7.70–7.64(m,9H),7.46–7.37(m,10H),7.24(d,J=2.0Hz,1H),7.19(d,J=8.7Hz,1H),4.00(s,3H). 13 C NMR(151MHz,Chloroform-d)δ162.7,154.1,150.5,135.0,134.6,133.6,132.4,129.8,129. 6,129.5,128.4,126.9,125.9,121.6,121.5,106.9,89.5,62.5.HRMS(ESI-TOF)m / z:[M+NH4] + Calculate for C 34 H 28 NO3Cl2Ge + ,642.0653found:642.0659.
[0042] Example 8
[0043] In a 25mL Schlenk tube, triphenylgermane (0.1mmol), high-valent iodine acetylene reagent (0.2mmol, 2.0 equivalents) and 9,10-phenanthrenequinone (5mol%) were dissolved in 1mL dimethyl sulfoxide. The reaction mixture was irradiated with a 10W430nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate (3×5mL) and saturated sodium chloride solution (3×5mL). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The obtained residue was purified by silica gel column chromatography using a petroleum ether / ethyl acetate mixed solvent as an eluent to finally obtain the target product.
[0044]
[0045] Purification by flash column chromatography (PE:EA, v / v=20:1). Colorless oil (28mg, 40% yield). 11H NMR (600 MHz, Chloroform-d) δ 7.70–7.63 (m, 6H), 7.55 (d, J = 8.4 Hz, 2H), 7.46–7.36 (m, 9H), 7.16 (d, J = 8.3 Hz, 2H), 6.93 (dd, J = 8.5, 4.2 Hz, 4H), 2.86 (dd, J = 10.6, 8.4 Hz, 1H), 1.95 (dd, J = 10.7, 7.4 Hz, 1H), 1.80 (t, J = 7.9 Hz, 1H), 1.75 (s, 6H). 13 13C NMR (151 MHz, Chloroform-d) δ 172.6, 154.9, 150.6, 135.0, 134.6, 133.4, 129.9, 129.6, 128.6, 128.4, 121.4, 121.1, 118.6, 107.0, 89.3, 79.3, 60.8, 34.8, 25.9, 25.5 (d, J = 2.6 Hz). HRMS (ESI-TOF) m / z: [M+Na] + calcd for C 39 H 32 O3NaCl2Ge + , 715.0832, found: 715.0838.
[0046] Example 9
[0047] In a 25 mL Schlenk tube, triphenylgermane (0.1 mmol), hypervalent iodine alkyne reagent (0.2 mmol, 2.0 equiv), and 9,10-phenanthrenequinone (5 mol%) were dissolved in 1 mL of dimethyl sulfoxide. The reaction mixture was irradiated with a 10 W 430 nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 h. After completion of the reaction, the reaction mixture was extracted with ethyl acetate (3 × 5 mL) and saturated sodium chloride solution (3 × 5 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The resulting residue was purified by silica gel column chromatography using a petroleum ether / ethyl acetate mixed solvent as the eluent to finally obtain the target product.
[0048]
[0049] Purification by flash column chromatography (PE:EA, v / v = 20:1). Colorless oil (36 mg, 52% yield). 11H NMR (600 MHz, Chloroform-d) δ 7.70–7.62 (m, 8H), 7.60–7.55 (m, 4H), 7.45–7.30 (m, 16H), 7.09 (d, J=8.6 Hz, 2H), 3.30 (t, J=7.3 Hz, 2H), 3.16 (t, J=7.3 Hz, 2H). 13 13C NMR (151 MHz, Chloroform-d) δ 170.3, 161.3, 148.2 (d, J=774.4 Hz), 135.1, 134.6, 133.4, 132.4, 129.5, 129.5, 128.9, 128.7, 128.6, 128.5, 128.4, 128.1, 127.9, 126.6, 121.6, 120.8, 107.2, 89.1, 31.3, 23.5. HRMS (ESI-TOF) m / z: [M+Na] + calcd for C 44 H 33 NO3NaGe + , 720.1564, found: 720.1568.
[0050] Example 10
[0051] In a 25 mL Schlenk tube, triphenylgermane (0.1 mmol), hypervalent iodine alkyne reagent (0.2 mmol, 2.0 equiv), and 9,10-phenanthrenequinone (5 mol%) were dissolved in 1 mL of dimethyl sulfoxide. The reaction mixture was irradiated with a 10 W 430 nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 h. After the reaction was completed, the reaction mixture was extracted with ethyl acetate (3×5 mL) and saturated sodium chloride solution (3×5 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The resulting residue was purified by silica gel column chromatography using a petroleum ether / ethyl acetate mixed solvent as the eluent to finally obtain the target product.
[0052]
[0053] Purification by flash column chromatography (PE:EA, v / v=20:1). Colorless oil (29 mg, 45% yield). 11H NMR (600 MHz, Chloroform-d) δ 8.32–8.17 (m, 2H), 8.07 (s, 2H), 7.74 (d, J = 8.3 Hz, 2H), 7.71–7.66 (m, 6H), 7.51 (d, J = 8.2 Hz, 1H), 7.48–7.41 (m, 10H), 7.36–7.30 (m, 1H), 7.30–7.26 (m, 1H), 2.94 (q, J = 7.5 Hz, 2H), 1.38 (t, J = 7.5 Hz, 3H). 13 13C NMR (151 MHz, Chloroform-d) δ 187.9, 167.4, 162.1, 153.7, 149.7, 139.1, 134.7, 134.6, 133.1, 132.5, 130.5, 129.7, 129.2, 128.5, 127.6, 126.3, 124.8, 124.0, 121.1, 118.4, 115.3, 111.2, 106.6, 94.1, 22.1, 12.2. HRMS (ESI-TOF) m / z: [[M+Na]] + calcd for C 44 H 30 O4NaBr2Ge + , 876.9615 found: 876.9531.
[0054] Example 11
[0055] In a 25 mL Schlenk tube, triphenylgermane (0.1 mmol), hypervalent iodine alkyne reagent (0.2 mmol, 2.0 equiv), and 9,10-phenanthrenequinone (5 mol%) were dissolved in 1 mL of dimethyl sulfoxide. The reaction mixture was irradiated with a 10 W 430 nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 h. After the reaction was completed, the reaction mixture was extracted with ethyl acetate (3 × 5 mL) and saturated sodium chloride solution (3 × 5 mL). The combined organic phases were dried over anhydrous sodium sulfate and the solvent was removed by rotary evaporation. The resulting residue was purified by silica gel column chromatography using a petroleum ether / ethyl acetate mixed solvent as the eluent to finally obtain the target product.
[0056]
[0057] Purification by flash column chromatography (PE:EA, v / v = 20:1). Colorless oil (29 mg, 45% yield). 11H NMR(600MHz,Chloroform-d)δ8.32–8.17(m,2H),8.07(s,2H),7.74(d,J=8.3Hz,2H),7.71–7.66(m,6H),7.51(d,J=8.2Hz,1H),7.48–7.41(m,10H),7.36–7.30(m,1H),7.30–7.26(m,1H),2.94(q,J=7.5Hz,2H),1.38(t,J=7.5Hz,3H). 13 13C NMR(151MHz,Chloroform-d)δ187.9,167.4,162.1,153.7,149.7,139.1,134.7,134.6,133.1,132.5,130.5,129.7,129.2,128.5,127.6,126.3,124.8,124.0,121.1,118.4,115.3,111.2,106.6,94.1,22.1,12.2.HRMS(ESI-TOF)m / z:[M+Na] + calcd forC 44 H 30 O4NaBr2Ge + ,876.9615found:876.9531.
[0058] Example 12
[0059] In a 25 mL Schlenk tube, triphenylgermane (0.1 mmol), hypervalent iodine yne reagent (0.2 mmol, 2.0 equiv), and 9,10-phenanthrenequinone (5 mol%) were dissolved in 1 mL of dimethyl sulfoxide. The reaction mixture was irradiated with a 10 W 430 nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 h. After the reaction was completed, the reaction mixture was extracted with ethyl acetate (3×5 mL) and saturated sodium chloride solution (3×5 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The resulting residue was purified by silica gel column chromatography using a petroleum ether / ethyl acetate mixed solvent as the eluent to obtain the target product finally.
[0060]
[0061] Purification by flash column chromatography(PE:EA,v / v=20:1).Colorless oil(33mg,60%yield). 11H NMR (600 MHz, Chloroform-d) δ 8.18 (d, J = 8.2 Hz, 2H), 7.73–7.63 (m, 8H), 7.48–7.38 (m, 9H), 7.30–7.23 (m, 1H), 7.15 (d, J = 7.9, 1.6 Hz, 1H), 7.06–6.95 (m, 2H). 13 13C NMR (151 MHz, Chloroform-d) δ 164.2, 151.3, 139.9, 134.8, 134.6, 132.2, 130.2, 129.7, 129.3, 128.5, 128.2, 127.0, 122.9, 120.8, 112.6, 106.9, 93.0, 55.9. HRMS (ESI-TOF) m / z: + calcd for C 34 H 26 O3NaGe + , 579.0986, found: 579.0980.
[0062] Example 13
[0063] In a 25 mL Schlenk tube, triphenylgermane (0.1 mmol), hypervalent iodine olefin reagent (0.2 mmol, 2.0 equiv), and 9,10-phenanthrenequinone (5 mol%) were dissolved in 1 mL of dimethyl sulfoxide. The reaction mixture was irradiated with a 10 W 430 nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate (3 × 5 mL) and saturated sodium chloride solution (3 × 5 mL). The combined organic phases were dried over anhydrous sodium sulfate and the solvent was removed by rotary evaporation. The resulting residue was purified by silica gel column chromatography using petroleum ether as the eluent to finally obtain the target product.
[0064]
[0065] Purification by flash column chromatography(PE).White solid(20mg,50%yield).1H NMR(600MHz,Chloroform-d)δ7.62–7.53(m,5H),7.50–7.45(m,3H),7.43–7.35(m,8H),7.35–7.26(m,4H),7.02(d,J=18.7Hz,1H),6.96(d,J=18.6Hz,1H).13C NMR(151MHz,Chloroform-d)δ146.8,136.4,135.1,134.8,129.1,128.6,128.3,128.1,126.6,124.0.
[0066] Example 14
[0067] In a 25 mL Schlenk tube, triphenylgermane hydride (0.1 mmol), hypervalent iodine nitrile reagent (0.2 mmol, 2.0 equiv), and 9,10-phenanthrenequinone (5 mol%) were dissolved in 1 mL of dimethyl sulfoxide. The reaction mixture was irradiated with a 10 W 430 nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 h. After the reaction was completed, the reaction mixture was extracted with ethyl acetate (3×5 mL) and saturated sodium chloride solution (3×5 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The resulting residue was purified by silica gel column chromatography using petroleum ether as the eluent to finally obtain the target product.
[0068]
[0069] Purification by flash column chromatography(PE:EA,v / v=10:1).Whitesolid(19mg,55%yield). 1 H NMR(600MHz,Chloroform-d)δ7.42(d,6H),7.32(t,3H),7.23(t,J=7.5Hz,6H). 13 CNMR(101MHz,Chloroform-d)δ141.7,133.2,131.9,127.9,94.5.HRMS(ESI-TOF)m / z:[M+NH4] + calcd for C 19 H 19 N2Ge + ,349.0755,found:349.0765.
[0070] Example 15
[0071] In a 25 mL Schlenk tube, triphenylgermane (0.1 mmol), hypervalent iodine benzene reagent (0.2 mmol, 2.0 equiv), and 9,10-phenanthrenequinone (5 mol%) were dissolved in 1 mL of dimethyl sulfoxide. The reaction mixture was irradiated with a 10 W 430 nm blue LED light source under a nitrogen atmosphere and stirred at room temperature for 12 h. After the reaction was completed, the reaction mixture was extracted with ethyl acetate (3 × 5 mL) and saturated sodium chloride solution (3 × 5 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The resulting residue was purified by silica gel column chromatography using petroleum ether as the eluent to finally obtain the target product.
[0072]
[0073] Purification by flash column chromatography(PE).White solid(21.4mg,56%yield). 1 HNMR(400MHz,Chloroform-d)δ7.81(d,J=8.0,1.5Hz,1H),7.66–7.57(m,1H),7.48(t,J=7.7Hz,1H). 13 C NMR(101MHz,Chloroform-d)δ137.8,132.2,129.9,128.2.HRMS(ESI-TOF)m / z:[M+NH4] + calcd for C 24 H 24 NGe + ,400.1115,found:400.1127.
[0074] Although the embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art can understand that various substitutions, changes, and modifications are possible without departing from the spirit and scope of the present invention and the appended claims. Therefore, the scope of the present invention is not limited to the content disclosed in the embodiments.
Claims
1. A method for preparing a visible light-induced organogermanium compound, characterized in that the steps Comprising: Germane hydride and hypervalent iodine reagent are dissolved in dimethyl sulfoxide, and then a photocatalyst 9,10-phenanthraquinone is added to the reaction system, and the reaction is carried out with stirring at room temperature. After the reaction is completed, extraction, drying, and rotary evaporation are performed to remove the organic solvent, and the target organogermanium compound is obtained by column chromatography separation.
2. The preparation method of an organogermanium compound induced by visible light according to claim 1, characterized in that, The reaction conditions are as follows: The reaction is carried out with stirring at room temperature under irradiation with 430 nm blue light in a nitrogen atmosphere.
3. A method for preparing a visible light-induced organogermanium compound according to claim 1, characterized in that: The structural formula of the described organogermanium compound is wherein R includes any one or more of phenyl or n-butyl, and FG includes any one or more of alkynyl, alkenyl, nitrile group or phenyl.
4. The preparation method of a visible light-induced organogermanium compound according to claim 1, characterized in that: The structural formula of the germane hydride described is Any one or more of them.
5. The preparation method of a visible light-induced organogermanium compound according to claim 1, characterized in that: The structural formula of the high-valent iodine reagent described above is wherein FG includes any one or more of alkynyl, alkenyl, nitrile group or phenyl group.
6. The preparation method of a visible light-induced organogermanium compound according to claim 1, characterized in that: The molar ratio of the germane hydride to the hypervalent iodine reagent is 1:
2.
7. A method for preparing a visible light-induced organogermanium compound according to claim 1, characterized in that: The molar fraction ratio of the germane hydride to the photocatalyst 9,10-phenanthraquinone is 1:5 mol%.
8. The preparation method of a visible light-induced organogermanium compound according to claim 1, characterized in that: The stirring time at room temperature is 12 h.
9. The preparation method of a visible light-induced organogermanium compound according to claim 1, characterized in that: In the column chromatography separation, the stationary phase is silica gel G, and the mobile phase is petroleum ether, cyclohexane, or a mixed solvent of petroleum ether / ethyl acetate.