A method for constructing CP bond between amine compounds and phosphorus oxide compounds

Abstract

The present invention discloses a method for constructing a C-P bond between an amine compound and a phosphorus oxide compound, comprising the following steps: 1) adding a photocatalyst to a solvent to obtain a solution A; 2) adding an amine compound and a phosphorus oxide compound to solution A to obtain a solution B; 3) irradiating solution B with a visible light source in an inert atmosphere, and the amine compound and the phosphorus oxide compound react to construct a C-P bond. The present invention realizes for the first time the construction of a C-P bond by a visible light-driven quantum dot-catalyzed reaction between an amine compound and a phosphorus oxide compound, and the reaction conditions are mild, and the light source can be irradiated to the quantum dot catalyst at room temperature and normal pressure, without the need for harsh reaction conditions such as high temperature and high pressure; at the same time, the reactants are simple, and no oxidant or free radical initiator is required, and the substrate does not need to be pre-activated, with fewer steps and atom economy.

Description

Technical Field

[0001] The present invention relates to the technical field of catalytic synthesis, and more specifically, to a method for constructing a CP bond between an amine compound and a phosphorus oxide compound. Background Art

[0002] Phosphorus-containing organic molecules are an important class of organic compounds, widely used in many fields such as medicine, pesticides, chemical biology, synthetic chemistry and materials chemistry. Therefore, it is of great synthetic significance to establish a simple and efficient method for synthesizing organophosphorus compounds. Among many methods, the construction of C-P bonds by visible light-catalyzed C-H / P-H direct cross-coupling is simple and direct. For example, in 2011, Magnus Rueping et al. used iridium-catalyzed C-H bond and P-H bond coupling reactions to synthesize α-aminophosphonates, in which O2 participated in the reaction as an oxidant (Chem. Commun. 2011, 47, 8679-8681); in 2021, Bing Yu et al. used the photocatalyst 4CzIPN- t Bu and the strong oxidant tert-butyl hydroperoxide achieve the phosphorylation reaction of isocyanide through a proton-coupled electron transfer process (J.Am.Chem.Soc.2021,143(2),964-972). These existing synthesis techniques usually require the help of oxidants. There are few reports on the construction of C-P bonds using photocatalysis in the absence of oxidants. For example, in 2019, our research group used alkyl cobalt oxime complexes as photocatalysts to efficiently achieve the coupling (addition) reaction of diaryl phosphine oxide with alkenes (alkynes) under visible light irradiation (J.Am.Chem.Soc.2019,141,13941-13947). Compared with traditional synthesis methods, this photocatalytic hydrogen release cross-coupling reaction avoids the use of oxidants, shortens the reaction steps, and has excellent step economy and atom economy. With the popularization of green chemistry and sustainable development concepts, it is a general trend to develop a new type of photocatalytic hydrogen release cross-coupling system that does not require the participation of free radical initiators and oxidants to construct C-P bonds.

[0003] Semiconductor quantum dots provide a new way to develop new photocatalytic systems to solve the above problems. Due to their excellent light-harvesting ability, adjustable band structure, abundant surface sites and multiple exciton generation, quantum dots (QDs) have become a new ideal photocatalyst for organic conversion (Chem. Eur. J. 2018, 24, 11530-11534; Chem. Soc. Rev. 2020, 49 (24), 9028-9056.). Previously, the applicant used quantum dots as photocatalysts to achieve important organic transformations such as the synthesis of disulfide compounds, the oxidation of alcohols, and the construction of carbon-carbon bonds and carbon-sulfur bonds without the need for oxidants and free radical initiators (Angew. Chem. Int. Ed. 2014, 53 (8), 2085-2089; Angew. Chem. Int. Ed. 2017, 56 (11), 3020-3024; Chem 2021, 7 (5), 1244-1257; Angew. Chem. Int. Ed. 2021, 60 (21), 11779-11783.). The applicant disclosed the construction of C-C bonds and C-S bonds in Chinese patents CN 201710326976.1 and CN 201810223387.5. On this basis, the present invention provides a method for photocatalytically constructing C-P bonds. Summary of the invention

[0004] An object of the present invention is to provide a method for constructing a CP bond between an amine compound and a phosphorus oxide compound, wherein the method realizes the construction of a C–P bond by photocatalytic C–H and P–H cross-coupling without the participation of an oxidant and free radicals.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A method for constructing a CP bond between an amine compound and a phosphorus oxide compound comprises the following steps:

[0007] 1) adding the photocatalyst into a solvent to obtain solution A;

[0008] 2) adding an amine compound and a phosphorus oxide compound to solution A to obtain solution B;

[0009] 3) In an inert atmosphere, solution B is irradiated with a visible light source, and the amine compound reacts with the phosphorus oxide compound to form a CP bond.

[0010] In the present invention, under the action of a photocatalyst, the CH bond at the nitrogen ortho position in the amine compound can be activated to generate a carbon free radical, the PH bond in the phosphorus oxide compound is activated to generate a phosphorus free radical, and the carbon free radical and the phosphorus free radical undergo a coupling reaction to finally form a C-P bond.

[0011] Preferably, there is at least one CH bond at the C1 position in the amine compound.

[0012] In the present invention, the carbon atom adjacent to nitrogen in the amino compound has at least one CH bond (C1), and the bond energy of the CH bond at C1 is weaker than that at C3 and more active, so it is more easily oxidized by the photocatalyst to participate in the reaction.

[0013] Preferably, the amine compound has a structural formula shown in Formula 1 or Formula 2:

[0014]

[0015] Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 Each is independently H, alkyl, alkoxy, phenyl, ester or halogen.

[0016] Preferably, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 Each is independently H, alkyl, alkoxy, phenyl or halogen.

[0017] Preferably, the alkyl group on the compound of formula 1 or formula 2 is CH3, CH2CH3; the alkoxy group is OCH3;

[0018] Preferably, in Formula 1: R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R7 , R 8 and R 9 independently H; or

[0019] R 7 For OCH3, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 and R 9 independently H; or

[0020] R 7 For CH3, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 and R 9 independently H; or

[0021] R 7 is CH2CH3, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 and R 9 independently H; or

[0022] R 7 is phenyl, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 and R 9 independently H; or

[0023] R 7 For F, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 and R 9 independently H; or

[0024] R 7 Cl, R 1 , R 2 , R 3 , R4 , R 5 , R 6 , R 8 and R 9 independently H; or

[0025] R 7 Br, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 and R 9 independently H; or

[0026] R 2 and R 3 Independent for OCH3, R 1 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Independent is H.

[0027] Preferably, in Formula 2: R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 Independent is H.

[0028] Preferably, the phosphorus oxide compound has a structural formula shown in Formula 3 or Formula 4:

[0029]

[0030] Among them, r 1 and r 2 is an alkyl group or a benzyl group,

[0031] r 3 、r 4 、r 5 、r 6 、r 7 、r 8 、r 9 、r 10 、r 11 and r 12 Each is independently hydrogen, alkyl, alkoxy, phenyl, ester or halogen.

[0032] Preferably, the alkyl group on the compound of formula 3 or formula 4 is a C1-C3 alkyl chain.

[0033] Preferably, in Formula 3: 1 and r 2 is independently benzyl; or,

[0034] r 1 and r 2 are independently CH2CH3; or;

[0035] r 1 and r 2 Independently is CH(CH3)2.

[0036] Preferably, r 3 ~r 12 All are H.

[0037] Preferably, the photocatalyst is selected from one or more of the following quantum dots: CdSe, CdS, CdTe, ZnSe, ZnS, CdSe / ZnS, CdSe / ZnO, CdSe / CdS, CdTe / CdSe, CdS / ZnSe, CdS / ZnTe, ZnSe / CdS or CuInS2.

[0038] The quantum dot photocatalyst in the present invention has the characteristics of excellent visible light response, multi-exciton generation, photogenerated charge separation and fast migration, and is a type of photocatalyst with broad application prospects. A possible implementation is that the molar concentration of the photocatalyst in solution B is between zero and saturation molar concentration, and does not include zero; more preferably, 1×10 -7 M~1×10 -3 M.

[0039] Preferably, a metal salt is also added to the solution A;

[0040] The metal salt is nickel chloride, ferric chloride, cobalt chloride, nickel sulfate, ferric sulfate, cobalt sulfate, nickel nitrate, ferric nitrate or cobalt nitrate; the metal salt solution in the present invention acts as a catalyst to increase the reaction rate.

[0041] Preferably, the concentration of the metal salt solution in solution A is ≥1×10 -4 mol / L. After the metal salt reaches saturation concentration in the solution, the content of the metal salt can be further increased, but it is theoretically of no economic value. Therefore, more preferably, the concentration of the metal salt solution is 1×10 -4 mol / L to saturation concentration; further, the concentration of the solution is 1×10 -4 mol / L~2.0mol / L.

[0042] The solvent in the present invention is only used to provide a solution environment for the reactants. Those skilled in the art are capable of selecting a suitable solvent, and the present invention does not impose any limitation on this.

[0043] Preferably, the solvent is an organic solvent;

[0044] Further preferably, the solvent is selected from one or more of acetonitrile, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, methanol, ethanol, isopropanol and tetrahydrofuran.

[0045] Preferably, the molar ratio of the amine compound to the phosphorus oxide compound in solution B is 1:0.01-100;

[0046] Preferably, the molar ratio of the amine compound to the phosphorus oxide compound in solution B is 1:0.1-10.

[0047] Preferably, the concentration of the amine compound in solution B is 1×10 -10 mmol / L~saturated concentration; the concentration of phosphorus oxide in solution B is 1×10 -10 mmol / L~saturated concentration.

[0048] The visible light source in the present invention is a light source that can provide stable visible light, and the present invention does not limit its type, for example, including but not limited to sunlight, LED lamp, mercury lamp or xenon lamp.

[0049] The beneficial effects of the present invention are as follows:

[0050] The present invention realizes for the first time the construction of CP bonds by the reaction of amine compounds and phosphorus oxide compounds driven by visible light, and the reaction conditions are mild. It can be achieved by irradiating the quantum dot catalyst with light source at room temperature and normal pressure, and does not require harsh reaction conditions such as high temperature and high pressure. At the same time, the reactants are simple, and no oxidant or free radical initiator is required. The substrate does not need to be pre-activated, the steps are few, and the atom economy is high. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings.

[0052] Figure 1 The hydrogen spectrum of the product dibenzyl (2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl) phosphonate in Example 1 of the present invention is shown.

[0053] Figure 2 The carbon spectrum of the product dibenzyl (2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl) phosphonate in Example 1 of the present invention is shown.

[0054] Figure 3 The phosphorus spectrum of dibenzyl (2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl) phosphonate, a product in Example 1 of the present invention, is shown.

[0055] Figure 4The hydrogen spectrum of the product dibenzyl (S)-(2-(4-methoxyphenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 4 of the present invention is shown.

[0056] Figure 5 The carbon spectrum of the product dibenzyl (S)-(2-(4-methoxyphenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 4 of the present invention is shown.

[0057] Figure 6 The phosphorus spectrum of dibenzyl (S)-(2-(4-methoxyphenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate, a product in Example 4 of the present invention, is shown.

[0058] Figure 7 The hydrogen spectrum of the product dibenzyl (S)-(2-p-tolyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 5 of the present invention is shown.

[0059] Figure 8 The carbon spectrum of the product dibenzyl (S)-(2-p-tolyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 5 of the present invention is shown.

[0060] Fig. 9 The phosphorus spectrum of the product dibenzyl (S)-(2-p-tolyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 5 of the present invention is shown.

[0061] Fig.10 The hydrogen spectrum of the product dibenzyl (S)-(2-(4-ethylphenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 6 of the present invention is shown.

[0062] Fig.11 The carbon spectrum of the product dibenzyl (S)-(2-(4-ethylphenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 6 of the present invention is shown.

[0063] Fig.12 The phosphorus spectrum of dibenzyl (S)-(2-(4-ethylphenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate, a product in Example 6 of the present invention, is shown.

[0064] Fig.13 The hydrogen spectrum of the product dibenzyl (S)-(2-([1,1'-biphenyl]-4-yl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 7 of the present invention is shown.

[0065] Fig.14The carbon spectrum of the product dibenzyl (S)-(2-([1,1'-biphenyl]-4-yl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 7 of the present invention is shown.

[0066] Fig.15 The phosphorus spectrum of dibenzyl (S)-(2-([1,1'-biphenyl]-4-yl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate, a product in Example 7 of the present invention, is shown.

[0067] Fig.16 The hydrogen spectrum of the product dibenzyl (S)-(2-(4-fluorophenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 8 of the present invention is shown.

[0068] Fig.17 The carbon spectrum of the product dibenzyl (S)-(2-(4-fluorophenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 8 of the present invention is shown.

[0069] Fig.18 The phosphorus spectrum of dibenzyl (S)-(2-(4-fluorophenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate, a product in Example 8 of the present invention, is shown.

[0070] Fig.19 The fluorine spectrum of the product dibenzyl (S)-(2-(4-fluorophenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 8 of the present invention is shown.

[0071] Fig. 20 The hydrogen spectrum of the product dibenzyl (S)-(2-(4-chlorophenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 9 of the present invention is shown.

[0072] Fig.21 The carbon spectrum of the product dibenzyl (S)-(2-(4-chlorophenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 9 of the present invention is shown.

[0073] Fig. 22 The phosphorus spectrum of dibenzyl (S)-(2-(4-chlorophenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate, a product in Example 9 of the present invention, is shown.

[0074] Fig.23 The hydrogen spectrum of the product dibenzyl (S)-(2-(4-bromophenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 10 of the present invention is shown.

[0075] Fig.24The carbon spectrum of the product dibenzyl (S)-(2-(4-bromophenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 10 of the present invention is shown.

[0076] Fig.25 The phosphorus spectrum of dibenzyl (S)-(2-(4-bromophenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate, the product in Example 10 of the present invention, is shown.

[0077] Fig.26 The hydrogen spectrum of the product dibenzyl (S)-(6,7-dimethoxy-2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 11 of the present invention is shown.

[0078] Fig. 27 The carbon spectrum of the product dibenzyl (S)-(6,7-dimethoxy-2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate in Example 11 of the present invention is shown.

[0079] Fig.28 The phosphorus spectrum of dibenzyl (S)-(6,7-dimethoxy-2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphonate, the product in Example 11 of the present invention, is shown.

[0080] Fig.29 The hydrogen spectrum of the product dibenzyl (S)-(5-phenyl-4,5,6,7-tetrahydrothiophene[3,2-c]pyridin-4-yl)phosphonate in Example 12 of the present invention is shown.

[0081] Fig.30 The carbon spectrum of the product dibenzyl (S)-(5-phenyl-4,5,6,7-tetrahydrothiophene[3,2-c]pyridin-4-yl)phosphonate in Example 12 of the present invention is shown.

[0082] Fig.31 The phosphorus spectrum of the product dibenzyl (S)-(5-phenyl-4,5,6,7-tetrahydrothiophene[3,2-c]pyridin-4-yl)phosphonate in Example 12 of the present invention is shown.

[0083] Fig.32 The hydrogen spectrum of the product (S) diphenyl(2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphine oxide in Example 13 of the present invention is shown.

[0084] Fig.33 The carbon spectrum of the product (S) diphenyl(2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphine oxide in Example 13 of the present invention is shown.

[0085] Fig.34The phosphorus spectrum of the product (S) diphenyl(2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphine oxide in Example 13 of the present invention is shown.

[0086] Fig.35 The hydrogen spectrum of the product diethyl (S)-(2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphine oxide in Example 14 of the present invention is shown.

[0087] Fig.36 The carbon spectrum of the product diethyl (S)-(2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphine oxide in Example 14 of the present invention is shown.

[0088] Fig.37 The phosphorus spectrum of diethyl (S)-(2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphine oxide, the product in Example 14 of the present invention, is shown.

[0089] Fig.38 The hydrogen spectrum of the product diisopropyl (S)-(2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphine oxide in Example 15 of the present invention is shown.

[0090] Fig.39 The carbon spectrum of the product diisopropyl (S)-(2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphine oxide in Example 15 of the present invention is shown.

[0091] Fig.40 The phosphorus spectrum of diisopropyl (S)-(2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phosphine oxide, the product in Example 15 of the present invention, is shown. DETAILED DESCRIPTION

[0092] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0093] Example 1

[0094] The synthesis of the compound dibenzyl (2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl) phosphonate is as follows:

[0095] 1) Take 4 mL of a solution with a concentration of 8.0×10 -5mol / L CdSe quantum dot aqueous solution, add 0.1mL of a mixed solution of 2mol / L nitric acid, centrifuge the mixed solution in a centrifuge, remove the upper aqueous solution, and obtain a solid substance; the purpose of this step is to (1) remove the ligands on the surface of the quantum dots; (2) remove the solvent water by centrifugal precipitation to obtain a solid substance, which is conducive to research with other solvents.

[0096] 2) adding 4 mL of acetonitrile to the solid substance in step 1) and ultrasonicating for 2 minutes to obtain a clear acetonitrile mixed solution;

[0097] 3) Add the mixed solution in step 2) to a 10 mL test tube, and add 0.1 mmol N-phenyltetrahydroisoquinoline, 0.2 mmol dibenzyl phosphite, and 200 μL NiCl2·6H2O (0.1 M) to the acetonitrile mixed solution to obtain a reaction solution;

[0098] 4) Under argon protection, the reaction solution in step 3) was irradiated with LED blue light for 18 hours;

[0099] 5) removing the reaction solvent by spin drying, and then separating by silica gel column to obtain the product dibenzyl (2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl) phosphonate.

[0100] The yield of the product was 90%. The product was identified as dibenzyl (2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl) phosphonate by H-NMR, C-NMR and P-NMR. Figure 1 , carbon spectrum see Figure 2 , phosphorus spectrum see Figure 3 .

[0101] 1 H NMR (400MHz, CDCl3) δ7.36–7.26(m,4H),7.27–7.18(m,8H),7.18–7.06(m,4H),6.96 (d,J=8.3Hz,2H),6.79(t,J=7.3Hz,1H),5.28(d,J=19.6Hz,1H),5.00(dd,J=11.6,7. 3Hz,1H),4.90(ddd,J=20.6,11.7,8.0Hz,2H),4.76(dd,J=11.7,7.7Hz,1H),4.01(dd d,J=12.9,8.5,4.8Hz,1H),3.70–3.50(m,1H),3.14–3.04(m,1H),3.02–2.87(m,1H). 13C NMR (101MHz, CDCl3) δ149.31(d,J=5.5Hz), 136.50(d,J=5.5Hz), 136.45(d,J=4.6Hz), 136.34(d,J= 6.0Hz),130.51(s),129.16(s),128.77(d,J=2.6Hz),128.40(s),128.32(s),128.23(s),128.20(s) ),128.18(s),128.11(s),127.97(d,J=4.6Hz),127.51(d,J=3.5Hz),125.94(d,J=2.9Hz),118.65( s), 114.99 (s), 68.55 (d, J = 7.3Hz), 67.74 (d, J = 7.8Hz), 59.07 (d, J = 157.4Hz), 43.62 (s), 26.86 (s). 31 P NMR (162MHz,CDCl3)δ24.38.

[0102] Example 2

[0103] The process of constructing the CP bond in Example 2 is compared with that in Example 1, except that NiCl2·6H2O is not added in step 3). The reaction also produces dibenzyl (2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl) phosphonate, but its yield is 69%, which is not as high as that in Example 1.

[0104] Comparative Example 1

[0105] The process of constructing the CP bond in Comparative Example 1 is compared with Example 1, except that the reaction process in step 4) is carried out in air. As a result, it is found that the reaction cannot proceed, indicating that the reaction of the CP bond in the present invention must be carried out in an inert atmosphere.

[0106] Example 3

[0107] The effect of different solvent types on the synthesis results was determined. The method steps were the same as in Example 1, except that the solvent in step 2) was changed from acetonitrile to N,N-dimethylformamide. Dibenzyl (2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl) phosphonate was also prepared in the reaction, but its yield was 34%, which was not as high as in Example 1.

[0108] Embodiment 4-12

[0109] In Examples 4-12, the reaction process of constructing the CP bond is exactly the same as that in Example 1, except that the type of the amine compound is changed. For details, see Table 1:

[0110] Table 1 Results obtained with different amine compounds

[0111]

[0112] Experiments show that when N-aryl tetrahydroisoquinoline contains different types of substituents such as alkyl, alkoxy, phenyl, and halogen, the reaction can obtain a very high yield, indicating that the substrate of the present invention has a wide range of applications. When the benzene ring contains a disubstituted alkoxy group, the reaction effect is still good. When 5-phenyl-4,5,6,7-tetrahydrothiophene [3,2-c] pyridine is used as a substrate, the reaction can also proceed well.

[0113] Examples 13-15

[0114] In Examples 13-15, the reaction process of constructing the CP bond is exactly the same as that in Example 1, except that the type of phosphorus oxide compound is changed. For details, see Table 2:

[0115] Table 2 Results obtained with different phosphorus oxide compounds

[0116]

[0117] Experiments have shown that different phosphorus oxide compounds can be coupled with N-aryltetrahydroisoquinoline to achieve C–P bond construction.

[0118] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A method for constructing a CP bond between an amine compound and a phosphorus oxide compound, characterized in that: The following steps are involved: 1) Add the photocatalyst into the solvent to obtain solution A; 2) adding an amine compound and a phosphorus oxide compound to solution A to obtain solution B; 3) In an inert atmosphere, irradiate solution B with a visible light source, and the amine compound reacts with the phosphorus oxide compound to form a CP bond; The amine compound has a structural formula shown in Formula 1 or Formula 2: Formula 1, Formula 2; Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 Each is independently H, CH3, CH2CH3, OCH3, phenyl or halogen; The phosphorus oxide compound has a structural formula shown in Formula 3 or Formula 4: Formula 3, Formula 4; Among them, r 1 and r 2 is a C1~C3 alkyl chain or a benzyl group, r 3 、r 4 、r 5 、r 6 、r 7 、r 8 、r 9 、r 10 、r 11 and r 12 Each independently is hydrogen or a C1~C3 alkyl chain; The photocatalyst is selected from CdSe quantum dots.

2. The method for constructing a CP bond according to claim 1, characterized in that: A metal salt is also added to the solution A.

3. The method for constructing a CP bond according to claim 2, characterized in that: The metal salt is nickel chloride, ferric chloride, cobalt chloride, nickel sulfate, ferric sulfate, cobalt sulfate, nickel nitrate, ferric nitrate or cobalt nitrate.

4. The method for constructing a CP bond according to claim 2, characterized in that: The concentration of metal salt solution in solution A is ≥1×10 -4 mol / L.

5. The method for constructing a CP bond according to claim 1, characterized in that: The solvent is acetonitrile, acetone, N,N -dimethylformamide, N,N - one or more of dimethylacetamide, methanol, ethanol, isopropanol and tetrahydrofuran.

6. The method for constructing a CP bond according to claim 1, characterized in that: The molar ratio of the amine compound to the phosphorus oxide compound in solution B is 1:0.01-100.

7. The method for constructing a CP bond according to claim 1, characterized in that: The concentration of quantum dots in solution A ranges from zero to saturation concentration, excluding zero; the concentration of amine compounds in solution B is 1×10 -10 mmol / L~saturated concentration; the concentration of phosphorus oxide in solution B is 1×10 -10 mmol / L~saturated concentration.

8. The method for constructing a CP bond according to claim 1, characterized in that: The visible light source is selected from sunlight, LED lamp, mercury lamp or xenon lamp.

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