A method for visible-light catalytic synthesis of organic boron compounds

Abstract

The present invention belongs to the technical fields of chemical pharmaceuticals and fine chemical preparations. Specifically, it relates to a method for the visible-light catalytic synthesis of organoboron compounds. This method uses aryl diazoacetate compounds and aminoborane adducts as raw materials, and under the irradiation of visible light, organoboron compounds are obtained. The novel method for the visible-light catalytic synthesis of organoboron compounds provided by the present invention provides a simple, efficient, and environmentally friendly new method for the synthesis of such compounds, and has wide applications in the technical fields of chemical pharmaceuticals and fine chemical preparations.

Description

Technical Field

[0001] The present invention belongs to the technical fields of chemical pharmaceuticals and fine chemical preparations, and particularly relates to a method for synthesizing organic boron compounds by visible light catalysis. Background Art

[0002] Organic boron compounds are widely used in the fields of organic synthesis, medicine, pesticides, materials, etc. Developing new C-B bond-forming reactions and efficiently synthesizing structurally diverse organic boron compounds have always received wide attention. The insertion reaction of carbenes into B-H bonds is an effective method for constructing C-B bonds. Currently, the insertion reaction of carbenes into B-H bonds using diazo compounds and boranes as raw materials is mainly realized by transition metal catalysis. For example, in 2013, the Zhou Qilin research group at Nankai University used a copper complex as a catalyst to achieve the B-H insertion reaction of aryl diazo esters and amino borane adducts, obtaining a series of organic boron compounds (JACS, 2013, 135, 14094).

[0003]

[0004] In recent years, visible light-catalyzed carbene transfer reactions have gradually become one of the research hotspots in the field of carbene chemistry. Compared with transition metal catalysis, visible light catalysis has the advantages of mild reaction conditions, simple operation, low cost, and environmental friendliness. There is little research on the B-H insertion reaction between diazo compounds and boranes under visible light catalysis. The present invention realizes the B-H insertion reaction between aryl diazoacetates and amino borane adducts through visible light catalysis, providing a practical, efficient, green, and environmentally friendly route for the synthesis of related organic boron compounds. Summary of the Invention

[0005] The present invention aims to provide a method for synthesizing organic boron compounds by visible light catalysis. Using various substituted aryl diazoacetates and amino borane adducts as raw materials, the reaction occurs under visible light irradiation to obtain the desired organic boron compounds. This reaction has a high yield, mild conditions, and simple operation. It provides a new method that is concise, efficient, green, and environmentally friendly for the synthesis of such compounds, and has wide applications in the technical fields of chemical pharmaceuticals and fine chemical preparations.

[0006] The above technical object of the present invention is achieved by the following technical solutions:

[0007] The present invention provides a method for synthesizing organic boron compounds by visible light catalysis. Under the action of visible light, aryl diazoacetates and amino borane adducts react to obtain organic boron compounds.

[0008] Among them, the molecular structural formula of the organic boron compound is as follows:

[0009]

[0010] Furthermore, R in the compound 1 is any one of various nitrogen heterocycles or tertiary amine structures, including but not limited to any one of heteroaryl, substituted heteroaryl, azacyclic group, N-substituted azacyclic group;

[0011] Heteroaryl includes but is not limited to one of pyridine, piperidine, pyrrole; The substituents in the substituted heteroaryl and N-substituted azacyclic group are each independently selected from at least one of alkyl, fluorine, chlorine, and haloalkyl.

[0012] Furthermore, R in the compound 2 is any one of aryl, heteroaryl, substituted aryl, and substituted heteroaryl; Aryl includes but is not limited to phenyl and naphthyl; Heteroaryl includes but is not limited to pyridyl and thienyl. The substituents in the substituted aryl and substituted heteroaryl are each independently selected from at least one of fluorine, chlorine, bromine, cyano, alkyl, aryl, haloalkyl, alkoxy, and aryloxy.

[0013] Furthermore, R in the compound 3 is any one of alkyl, aryl, substituted aryl, and allyl.

[0014] Furthermore, a method for photocatalytic synthesis of an organoboron compound provided by the present invention has a reaction equation as shown below:

[0015]

[0016] In the above reaction equation, the structural formula of the aryldiazoacetate (Compound 1) is one of the following:

[0017]

[0018] In the above reaction equation, the aminoborane adduct (Compound 2) is one of the following:

[0019]

[0020] Furthermore, the molar ratio of the aryldiazoacetate to the aminoborane adduct is 1:2 to 1:6.

[0021] Furthermore, the concentration of the aryldiazoacetate is 0.05 to 0.4 moL / L.

[0022] Furthermore, the solvent is dichloromethane, 1,2-dichloroethane, ethyl acetate, and chloroform.

[0023] Furthermore, the wavelength of the visible light is 450 to 500 nanometers.

[0024] Furthermore, the reaction time is 5 to 24 hours, and the reaction temperature is room temperature.

[0025] In summary, the present invention has the following beneficial effects:

[0026] A method for the visible-light catalytic synthesis of organic boron compounds provided by the present invention does not require the addition of any catalysts and additives, and only needs to be irradiated with visible light to react. It has low cost, is relatively green and environmentally friendly. At the same time, the reaction conditions are very mild, the operation is very simple, which is conducive to subsequent large-scale industrial synthesis. The present invention provides a practical technical route for the synthesis of related organic boron compounds. Specific Embodiments

[0027] The present invention will be further described below by way of examples.

[0028] The following non-limiting examples are used to explain and illustrate the present invention, rather than to limit the present invention. Any modifications and changes made to the present invention within the spirit and scope of the claims of the present invention fall within the protection scope of the present invention. The reagents, catalysts, and solvents used in the present invention were all commercially purchased or synthesized according to the literature reports, and the solvents were refined and purified before use.

[0029] Example 1

[0030]

[0031] At room temperature, 35.2 mg (0.2 mmol, 1 eq) of methyl phenylacetate diazo (a1) and 121.11 mg (1 mmol, 5 eq) of 3,5-dimethylpyridine borane (b1) were added to dichloromethane (DCM) (2 mL), and stirred under 470 nm blue light for 12 h. After concentration, it was separated and purified by column chromatography (the eluent was V(PE):V(EA)=5:1) to obtain the product L1, a white solid, with a yield of 87%. 1 H NMR (400 MHz, CDCl3) δ 7.80 (s, 2H), 7.50 (s, 1H), 7.19–7.12 (m, 4H), 7.05–7.01 (m, 1H), 3.59 (s, 3H), 3.33 (t, J = 5.0 Hz, 1H), 2.26 (s, 6H). 13 C NMR (100 MHz, CDCl3) δ 178.2, 144.7, 142.9, 141.3, 134.9, 128.0, 127.6, 124.4, 50.9, 18.3. HRMS (ESI) m / z: calcd for C 16 H 20 BNNaO2 + [M+Na] + 292.1479, found 292.1485.

[0032] Example 2

[0033] Under the same conditions as in Example 1, the amount of 3,5-dimethylpyridine borane was changed from 5 equivalents to 3 equivalents, and product L1 was obtained with a yield of 81%.

[0034] Under the same conditions as in Example 1, the amount of 3,5-dimethylpyridine borane was changed from 5 equivalents to 6 equivalents, and product L1 was obtained with a yield of 86%.

[0035] Under the same conditions as in Example 1, the amount of 3,5-dimethylpyridine borane was changed from 5 equivalents to 2 equivalents, and product L1 was obtained with a yield of 67%.

[0036] Example 3

[0037] Under the same conditions as in Example 1, the amount of DCM was changed from 2 mL to 0.5 mL, and product L1 was obtained with a yield of 82%.

[0038] Example 4

[0039] Under the same conditions as in Example 1, DCM was changed to DCE, and product L1 was obtained with a yield of 81%.

[0040] Under the same conditions as in Example 1, DCM was changed to ethyl acetate, and product L1 was obtained with a yield of 68%.

[0041] Under the same conditions as in Example 1, DCM was changed to chloroform, and product L1 was obtained with a yield of 66%.

[0042] Under the same conditions as in Example 1, DCM was changed to n-hexane, and product L1 was obtained with a yield of 10%.

[0043] Example 5

[0044]

[0045] Under the same conditions as in Example 1, 3,5-dimethylpyridine borane was changed to 3,5-difluoropyridine borane (b2), and product L2, a white solid, was obtained with a yield of 62%. 1 H NMR(400MHz,CDCl3)δ7.98(s,2H),7.53-7.49(m,1H),7.19-7.14(m,4H),7.09-7.05(m,1H),3.63(s,3H),3.41(t,J=4.6Hz,1H). 1313C NMR(100MHz,CDCl3)δ177.9,160.5,160.4,157.9,157.8,141.9,134.0,133.6,133.6,128.7,128.1,127.6,126.7,124.9,116.3,116.1,115.9,51.2.HRMS(ESI)m / z:calcd for C 14 H 20 BF2NNaO2 + [M+Na] + 300.0978,found 300.0986.

[0046] Example 6

[0047]

[0048] Under the same conditions as in Example 1, 3,5-dimethylpyridine borane was replaced with 3-chloropyridine borane (b3) to obtain product L3, a pale yellow solid, with a yield of 86%. 1 1H NMR(400MHz,CDCl3)δ8.13(d,J=2.3Hz,1H),8.10(d,J=5.6Hz,1H),7.91-7.88(m,1H),7.35(dd,J=8.2,5.7Hz,1H),7.18-7.14(m,4H),7.08–7.03(m,1H),3.60(s,3H),3.38(t,J=4.7Hz,1H). 13 13C NMR(100MHz,CDCl3)δ178.0,146.7,145.5,142.2,140.0,133.0,127.9,127.8,125.5,124.7,51.0.HRMS(ESI)m / z:calcd forC 14 H 15 BClNNaO2 + [M+Na] + 298.0776,found 298.0784.

[0049] Example 7

[0050]

[0051] Under the same conditions as in Example 1, 3,5-dimethylpyridine borane was replaced with 3-trifluoromethylpyridine borane (b4) to obtain product L4, a white solid, with a yield of 83%. 11H NMR (400 MHz, CDCl3) δ 8.42 (d, J = 5.8 Hz, 1H), 8.30 (s, 1H), 8.18 (d, J = 8.0 Hz, 1H), 7.60 (dd, J = 8.0, 5.7 Hz, 1H), 7.16–7.03 (m, 5H), 3.62 (s, 3H), 3.44 (t, J = 4.4 Hz, 1H). 13 13C NMR (100 MHz, CDCl3) δ 178.0, 150.6, 145.0, 144.9, 142.0, 137.3, 137.2, 128.8, 128.4, 128.1, 127.5, 125.3, 124.8, 51.1. HRMS (ESI) m / z: calcd for C 15 H 15 BF3NNaO2 + [M+Na] + 332. 1040, found 332. 1048.

[0052] Example 8

[0053]

[0054] Under the same conditions as in Example 1, 3,5-dimethylpyridine borane was replaced with pyridine borane (b5) to obtain product L5, a pale yellow oily liquid with a yield of 84%. 1 1H NMR (400 MHz, CDCl3) δ 8.20–8.18 (m, 2H), 7.94–7.89 (m, 1H), 7.40 (dd, J = 7.7 Hz, 2.6 Hz, 2H), 7.18–7.10 (m, 4H), 7.05–7.01 (m, 1H), 3.59 (s, 3H), 3.38 (t, J = 4.9 Hz, 1H). 13 13C NMR (100 MHz, CDCl3) δ 178.2, 147.4, 142.6, 140.2, 127.9, 127.8, 125.0, 124.5, 51.0, 14.3. HRMS (ESI) m / z: calcd for C 14 H 16 BNNaO2 + [M+Na] + 264. 1166, found 264. 1174.

[0055] Example 9

[0056]

[0057] Under the same conditions as in Example 1, 3,5-dimethylpyridine borane was replaced with 1-methylazacyclohexane borane (b6) to obtain product L6, a pale yellow solid, with a yield of 83%. 1 H NMR(400MHz,CDCl3)δ7.45-7.42(m,2H),7.23(td,J=7.8,3.2Hz,2H),7.11–7.09(m,1H),3.60(m,3H),3.25(t,J=3.9Hz,1H),3.00-2.94(m,1H),2.85-2.78(m,1H),2.72–2.67(m,1H),2.59–2.54(m,1H),2.46(m,3H),1.82–1.41(m,6H). 13 C NMR(100MHz,CDCl3)δ179.0,144.0,129.2,127.9,124.9,58.8,58.7,51.3,46.2,22.7,20.2,20.1.HRMS(ESI)m / z:calcd for C 15 H 24 BNNaO2 + [M+Na] + 284.1792,found284.1799.

[0058] Example 10

[0059]

[0060] Under the same conditions as in Example 1, 3,5-dimethylpyridine borane was replaced with N-methylcyclopentane borane (b7) to obtain product L7, a white solid, with a yield of 84%. 1 H NMR(400MHz,CDCl3)δ7.46–7.44(m,2H),7.27–7.23(m,2H),7.13–7.09(m,1H),3.63(s,3H),3.29(t,J=4.9Hz,1H),3.21–3.14(m,1H),2.99–2.92(m,1H),2.86–2.79(m,1H),2.59–2.54(m,1H),2.53(s,3H),2.02–1.85(m,4H). 13 C NMR(100MHz,CDCl3)δ178.9,143.7,129.2,127.9,125.0,61.8,61.7,51.3,47.7,22.4,22.3.HRMS(ESI)m / z:calcd for C 14 H 22 BNNaO2 +[M+Na] + 270.1636, found 270.1642.

[0061] Example 11

[0062]

[0063] Under the same conditions as in Example 1, change the diazo of methyl phenylacetate to isobutyl phenylacetate diazo (a2) to obtain product L8, a pale yellow oily liquid, with a yield of 67%. 1 H NMR(400MHz, CDCl3) δ 7.82(s, 2H), 7.50(s, 1H), 7.21–7.18(m, 2H), 7.14(t, J = 7.6Hz, 2H), 7.05–7.01(m, 1H), 3.77(d, J = 6.7Hz, 2H), 3.35(t, J = 4.9Hz, 1H), 2.26(s, 6H), 1.92–1.82(m, 1H), 0.90(d, J = 6.6Hz, 6H). 13 C NMR(100MHz, CDCl3) δ 177.9, 144.8, 143.2, 141.2, 134.9, 128.1, 127.6, 124.3, 69.7, 28.0, 19.4, 18.3. HRMS(ESI) m / z: calcd for C 19 H 26 BNNaO2 + [M+Na] + 334.1949, found 334.1957.

[0064] Example 12

[0065]

[0066] Under the same conditions as in Example 1, change the diazo of methyl phenylacetate to allyl phenylacetate diazo (a3) to obtain product L9, a white solid, with a yield of 75%. 1 H NMR(400MHz, CDCl3) δ 7.82(s, 2H), 7.50(s, 1H), 7.21–7.18(m, 2H), 7.15(t, J = 7.3Hz, 2H), 7.06–7.02(m, 1H), 5.93–5.84(m, 1H), 5.28(dd, J = 17.2, 1.8Hz, 1H), 5.16(dd, J = 10.5, 1.6Hz, 1H), 4.52–4.50(m, 2H), 3.37(t, J = 4.9Hz, 1H), 2.26(s, 6H). 1313C NMR (100 MHz, CDCl3) δ 177.4, 144.8, 142.9, 141.2, 134.9, 133.4, 128.1, 127.6, 124.4, 117.3, 64.2, 18.3. HRMS (ESI) m / z: calcd for C 18 H 22 BNNaO2 + [M+Na] + 318.1636, found 318.1642.

[0067] Example 13

[0068]

[0069] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with benzyl phenylacetate diazo (a4) to obtain product L10, a pale yellow solid, with a yield of 76%. 1 1H NMR (400 MHz, CDCl3) δ 7.6 (s, 2H), 7.43 (s, 1H), 7.37–7.29 (m, 5H), 7.22-7.20 (m, 2H), 7.16 (t, J = 7.6 Hz, 2H), 7.05 (t, J = 7.1 Hz, 1H), 5.05 (dd, J = 28.7, 12.6 Hz, 2H), 3.44 (t, J = 4.8 Hz, 1H), 2.19 (s, 6H). 13 13C NMR (100 MHz, CDCl3) δ 177.5, 144.7, 142.9, 141.2, 137.4, 134.8, 128.4, 128.1, 128.1, 127.7, 127.6, 124.4, 65.2, 18.2. HRMS (ESI) m / z: calcd for C 22 H 24 BNNaO2 + [M+Na] + 368.1792, found 368.1804.

[0070] Example 14

[0071]

[0072] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 2-fluorophenylacetate diazo (a5) to obtain product L11, a white solid, with a yield of 78%. 11H NMR (400 MHz, CDCl3) δ 7.91 (s, 2H), 7.71 - 7.67 (m, 1H), 7.54 (s, 1H), 7.04–6.97 (m, 2H), 6.84–6.79 (m, 1H), 3.70 (t, J = 5.2 Hz, 1H), 3.57 (s, 3H), 2.28 (s, 6H). 13 13C NMR (101 MHz, CDCl3) δ 177.7, 160.9, 158.5, 144.7, 141.4, 135.1, 130.5, 130.4, 129.9, 129.7, 125.6, 125.6, 123.4, 123.4, 114.3, 114.0, 51.0, 18.3. HRMS (ESI) m / z: calcd for C 16 H 19 BFNNaO2 + [M + Na] + 310.1385, found 310.1395.

[0073] Example 15

[0074]

[0075] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 3 - fluorophenylacetate diazo (a6) to obtain product L12, a pale yellow solid, with a yield of 42%. 1 1H NMR (400 MHz, CDCl3) δ 7.81 (s, 2H), 7.54 (s, 1H), 7.11 - 7.06 (m, 1H), 6.96 (dt, J = 11.0, 2.0 Hz, 1H), 6.91 (d, J = 9.2 Hz, 1H), 6.72 (td, J = 8.5, 2.6 Hz, 1H), 3.59 (s, 3H), 3.34 (t, J = 4.8 Hz, 1H), 2.29 (s, 6H). 13 13C NMR (100 MHz, CDCl3) δ 177.8, 161.5, 145.8, 145.7, 144.8, 141.5, 135.1, 128.8, 128.8, 123.7, 123.7, 114.9, 114.6, 111.2, 110.9, 51.0, 18.3. HRMS (ESI) m / z: calcd for C 16 H 19 BFNNaO2 + [M + Na] + 310.1385, found 310.1395.

[0076] Example 16

[0077]

[0078] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 4-fluorophenylacetate diazo (a7) to obtain product L13, a white solid, with a yield of 83%. 1 H NMR(400MHz,CDCl3)δ7.84(s,2H),7.53(s,1H),7.17–7.13(m,2H),6.83(t,J=8.9Hz,2H),3.56(s,3H),3.30(t,J=5.0Hz,1H),2.28(s,6H). 13 C NMR(100MHz,CDCl3)δ178.2,161.7,159.3,144.6,141.4,138.5,138.5,135.1,129.4,129.3,114.3,114.1,50.9,18.3.HRMS(ESI)m / z:calcd for C 16 H 19 BFNNaO2 + [M+Na] + 310.1385,found 310.1395.

[0079] Example 17

[0080]

[0081] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 2-chlorophenylacetate diazo (a8) to obtain product L14, a light yellow solid, with a yield of 86%. 1 H NMR(400MHz,CDCl3)δ7.92(s,2H),7.80(dd,J=8.1,1.6Hz,1H),7.54(s,1H),7.19–7.14(m,2H),7.00–6.96(m,1H),3.94–3.91(m,1H),3.58(s,3H),2.29(s,6H). 13 C NMR(100MHz,CDCl3)δ177.7,144.9,141.4,140.3,135.1,132.9,130.7,128.5,126.3,125.6,51.1,18.4.HRMS(ESI)m / z:calcd for C 16 H 19 BClNNaO2 + [M+Na] + 326.1089,found 326.1097.

[0082] Example 18

[0083]

[0084] Under the same conditions as in Example 1, methyl phenylacetate diazonium was replaced with methyl m-chlorophenylacetate diazonium (a9) to obtain product L15 as a pale yellow solid in a yield of 45%. 1 H NMR (400MHz, CDCl3) δ7.80 (s, 2H), 7.56 (s, 1H), 7.12-7.06 (m, 3H), 7.03-7.00 (m, 1H), 3.59 (s, 3H), 3.32 (t, J = 4.8Hz, 1H), 2.30 (s, 6H). 13 C NMR(100MHz, CDCl3)δ177.7,145.2,144.8,141.5,135.1,133.4,128.9,127.9,126.3,124.4,51.1,18.4.HRMS(ESI)m / z:calcd for C 16 H 19 BClNNaO2 + [M+Na] + 326.1089, found 326.1097.

[0085] Example 19

[0086]

[0087] Under the same conditions as in Example 1, methyl phenylacetate diazonium was replaced with methyl p-chlorophenylacetate diazonium (a10) to obtain product L16 as a white solid in a yield of 73%. 1 H NMR (400MHz, (CD3)2SO) δ 8.04 (s, 2H), 7.87 (s, 1H), 7.18 (s, 4H), 3.36 (s, 3H), 3.26 (t, J = 5.2Hz, 1H), 2.30 (s, 6H). 13 CNMR(100MHz,(CD3)2SO)δ176.9,144.2,142.1,142.0,135.5,129.8,128.6,127.2,50.3,48.0,17.6.HRMS(ESI)m / z:calcdfor C 16 H 19 BClNNaO2 + [M+Na] + 326.1089, found 326.1097.

[0088] Example 20

[0089]

[0090] Under the same conditions as in Example 1, the diazo of methyl phenylacetate was replaced with the diazo of methyl 2-bromophenylacetate (a11), and the product L17, a white solid, was obtained with a yield of 75%. 1 H NMR(400MHz,CDCl3)δ7.91(s,2H),7.80(dd,J=7.9,1.8Hz,1H),7.53(s,1H),7.35(dd,J=8.0,1.4Hz,1H),7.21(td,J=7.5,1.3Hz,1H),6.89(td,J=7.4,1.8Hz,1H),3.92-3.89(m,1H),3.57(s,3H),2.28(s,6H). 13 C NMR(100MHz,CDCl3)δ177.6,144.9,141.9,141.4,135.1,131.8,130.9,126.9,126.0,124.2,51.1,18.3.HRMS(ESI)m / z:calcd for C 16 H 19 BBrNNaO2 + [M+Na] + 370.0584,found 370.0588.

[0091] Example 21

[0092]

[0093] Under the same conditions as in Example 1, the diazo of methyl phenylacetate was replaced with the diazo of methyl 3-bromophenylacetate (a12), and the product L18, a white solid, was obtained with a yield of 66%. 1 H NMR(400MHz,(CD3)2SO)δ8.03(s,2H),7.88(s,1H),7.37(t,J=1.8Hz,1H),7.21(dt,J=7.6,1.6Hz,1H),7.14(dt,J=7.8,1.5Hz,1H),7.09(t,J=7.7Hz,1H),3.37(s,3H),3.27(t,J=1.8Hz,1H),2.31(s,6H). 13 C NMR(100MHz,(CD3)2SO)δ176.7,145.9,144.2,142.2,135.5,130.5,129.5,127.0,126.9,120.9,50.4,48.3,17.6.HRMS(ESI)m / z:calcd for C16 H 19 BBrNNaO2 + [M+Na] + 370.0584, found 370.0588.

[0094] Example 22

[0095]

[0096] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 4-bromophenylacetate diazo (a13) to obtain product L19, a pale yellow solid, with a yield of 80%. 1 H NMR(400MHz,(CD3)2SO)δ8.03(s,2H),7.86(s,1H),7.32–7.29(m,2H),7.15–7.11(m,2H),3.36(s,3H),3.25(t,J=5.2Hz,1H),2.3(s,6H). 13 C NMR(100MHz,(CD3)2SO)δ176.8,144.2,142.5,142.1,135.5,130.2,130.1,117.0,50.3,17.6.HRMS(ESI)m / z:calcd for C 16 H 19 BBrNNaO2 + [M+Na] + 370.0584, found 370.0588.

[0097] Example 23

[0098]

[0099] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 3-(trifluoromethyl)phenylacetate diazo (a14) to obtain product L20, a white solid, with a yield of 63%. 1 H NMR(400MHz,CDCl3)δ7.77(s,2H),7.54(s,1H),7.50-7.47(m,1H),7.31–7.27(m,3H),3.60(s,3H),3.41(t,J=4.9Hz,1H),2.27(s,6H). 1313C NMR (100 MHz, CDCl3) δ 177.7, 144.7, 144.1, 141.6, 135.3, 131.6, 129.8, 129.5, 128.1, 124.3, 124.2, 123.2, 121.1, 121.0, 51.1, 18.2. HRMS (ESI) m / z: calcd for C 17 H 19 BF3NNaO2 + [M+Na] + 360.1353, found 360.1363.

[0100] Example 24

[0101]

[0102] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 4-cyanophenylacetate diazo (a15) to obtain product L21, a pale yellow solid, with a yield of 43%. 1 1H NMR (400 MHz, CDCl3) δ 7.82 (s, 2H), 7.57 (s, 1H), 7.43 (d, J = 8.5 Hz, 2H), 7.32 (d, J = 8.4 Hz, 2H), 3.57 (s, 3H), 3.40 (t, J = 4.9 Hz, 1H), 2.31 (s, 6H). 13 13C NMR (100 MHz, CDCl3) δ 177.2, 149.3, 144.6, 141.8, 135.4, 132.4, 131.5, 128.6, 127.4, 119.8, 107.7, 51.1, 18.4. HRMS (ESI) m / z: calcd for C 17 H 19 BN2NaO2 + [M+Na] + 317.1432, found 317.1438.

[0103] Example 25

[0104]

[0105] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 2,4-dichlorophenylacetate diazo (a16) to obtain product L22, a white solid, with a yield of 79%. 1HNMR(400MHz,CDCl3)δ7.94(s,2H),7.75(d,J=8.5Hz,1H),7.56(s,1H),7.19(d,J=2.2Hz,1H),7.14(dd,J=8.6,2.3Hz,1H),3.85(t,J=5.2Hz,1H),3.55(s,3H),2.31(s,6H). 13 C NMR(100MHz,CDCl3)δ177.4,144.8,141.6,139.1,135.3,133.3,131.6,130.3,128.1,126.5,51.1,18.3.HRMS(ESI)m / z:calcd for C 16 H 18 BCl2NNaO2 + [M+Na] + 360.0700,found 360.0708.

[0106] Example 26

[0107]

[0108] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 3,4-dichlorophenylacetate diazo (a17) to obtain product L23, a pale yellow solid, with a yield of 61%. 1 H NMR(400MHz,CDCl3-d)δ7.83(s,2H),7.58(s,1H),7.24–7.21(m,2H),7.08(dd,J=8.4,2.1Hz,1H),3.57(s,3H),3.29(t,J=4.9Hz,1H),2.32(s,6H). 13 C NMR(100MHz,CDCl3)δ177.5,144.7,143.6,141.7,135.3,131.3,129.7,129.4,127.9,127.7,51.0,18.4.HRMS(ESI)m / z:calcd for C 16 H 18 BCl2NNaO2 + [M+Na] + 360.0700,found 360.0708.

[0109] Example 27

[0110]

[0111] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 2-chloro-4-bromophenylacetate diazo (a18) to obtain product L24, a white solid, with a yield of 77%. 1 H NMR(400MHz,CDCl3)δ7.94(s,2H),7.70(d,J=8.5Hz,1H),7.57(s,1H),7.34(d,J=2.1Hz,1H),7.28(dd,J=8.5,2.2Hz,1H),3.84(t,J=5.2Hz,1H),3.55(s,3H),2.32(s,6H). 13 C NMR(100MHz,CDCl3)δ177.3,144.8,141.6,139.6,135.3,133.6,132.0,130.8,129.4,117.9,51.1,18.4.HRMS(ESI)m / z:calcd for C 16 H 18 BBrClNNaO2 + [M+Na] + 404.0194,found404.0199.

[0112] Example 28

[0113]

[0114] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 2-chloro-4-fluorophenylacetate diazo (a19) to obtain product L25, a white solid, with a yield of 83%. 1 H NMR(400MHz,CDCl3)δ7.95(s,2H),7.78(dd,J=8.7,6.5Hz,1H),7.56(s,1H),6.94–6.88(m,2H),3.83(t,J=5.2Hz,1H),3.54(s,3H),2.31(s,6H). 13 C NMR(100MHz,CDCl3)δ177.7,161.0,158.6,144.8,141.6,136.2,136.2,135.3,133.0,132.9,131.6,131.6,115.5,115.3,113.5,113.3,51.0,18.3.HRMS(ESI)m / z:calcdfor C 16 H 18 BClFNNaO2 + [M+Na] + 344.0995,found 344.1003.

[0115] Example 29

[0116]

[0117] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 3,4 - dimethoxyphenylacetate diazo (a20) to obtain product L26, a pale yellow solid, with a yield of 58%. 1 H NMR(400MHz,CDCl3)δ7.84(s,2H),7.52(s,1H),6.92(d,J=2.0Hz,1H),6.66(d,J=8.2Hz,1H),6.60(dd,J=8.2,2.0Hz,1H),3.80(s,3H),3.79(s,3H),3.56(s,3H),3.26(t,J=4.8Hz,1H),2.28(s,6H). 13 C NMR(100MHz,CDCl3)δ178.5,148.3,146.1,144.8,141.2,135.7,134.9,119.8,111.7,110.7,56.0,55.7,50.9,18.3.HRMS(ESI)m / z:calcd for C 18 H 24 BNNaO4 + [M+Na] + 352.1690,found 352.1700.

[0118] Example 30

[0119]

[0120] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl m - methoxyphenylacetate diazo (a21) to obtain product L27, a white solid, with a yield of 80%. 1 H NMR(400MHz,CDCl3)δ7.81(s,2H),7.52(s,1H),7.04(t,J=7.9Hz,1H),6.83 - 6.82(m,1H),6.71(d,J=7.6Hz,1H),6.61 - 6.58(m,1H),3.72(s,3H),3.59(s,3H),3.32(t,J=4.8Hz,1H),2.27(s,6H). 1313C NMR(100MHz,CDCl3)δ178.1,159.2,144.7,144.6,141.3,134.9,128.4,120.5,113.2,110.2,55.1,50.9,18.3.HRMS(ESI)m / z:calcd for C 17 H 22 BNNaO3 + [M+Na] + 322.1585,found 322.1594.

[0121] Example 31

[0122]

[0123] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl p-methoxyphenylacetate diazo (a22) to obtain product L28, a white solid, with a yield of 82%. 1 1H NMR(400MHz,CDCl3)δ7.86(s,2H),7.52(s,1H),7.13–7.09(m,2H),6.74–6.70(m,2H),3.74(s,3H),3.56(s,3H),3.26(t,J=5.0Hz,1H),2.28(s,6H). 13 13C NMR(100MHz,CDCl3)δ178.5,156.8,144.7,141.2,135.0,134.9,129.1,113.2,55.3,50.9,18.3.HRMS(ESI)m / z:calcd for C 17 H 22 BNNaO3 + [M+Na] + 322.1585,found322.1594.

[0124] Example 32

[0125]

[0126] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl o-methylphenylacetate diazo (a23) to obtain product L29, a light red solid, with a yield of 60%. 11H NMR (400 MHz, CDCl3) δ 7.81 (s, 2H), 7.53 (s, 1H), 7.38 (dd, J = 7.6, 1.6 Hz, 1H), 7.06–6.94 (m, 3H), 3.59–3.58 (m, 1H), 3.57 (s, 3H), 2.28 (s, 6H), 2.20 (s, 3H). 13 13C NMR (100 MHz, CDCl3) δ 178.5, 145.0, 141.3, 140.8, 134.8, 134.7, 129.7, 128.0, 125.3, 124.3, 50.9, 20.2, 18.3. HRMS (ESI) m / z: calcd for C 17 H 22 BNNaO2 + [M + Na] + 306.1636, found 306.1642.

[0127] Example 33

[0128]

[0129] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 3-methylphenylacetate diazo (a24) to obtain product L30, a white solid, with a yield of 85%. 1 1H NMR (400 MHz, CDCl3) δ 7.82 (s, 2H), 7.52 (d, J = 1.1 Hz, 1H), 7.04 (t, J = 7.6 Hz, 1H), 7.00 (s, 1H), 6.96 (d, J = 7.8 Hz, 1H), 6.86 (d, J = 7.5 Hz, 1H), 3.57 (s, 3H), 3.30 (t, J = 4.9 Hz, 1H), 2.27 (s, 6H), 2.24 (s, 3H). 13 13C NMR (100 MHz, CDCl3) δ 178.3, 144.8, 142.8, 141.2, 137.0, 134.8, 128.7, 127.6, 125.2, 125.1, 50.9, 21.6, 18.3. HRMS (ESI) m / z: calcd for C 17 H 22 BNNaO2 + [M + Na] + 306.1636, found 306.1642.

[0130] Example 34

[0131]

[0132] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 4-methylphenylacetate diazo (a25) to obtain product L31, a white solid, with a yield of 68%. 1 H NMR(400MHz,CDCl3)δ7.84(s,2H),7.51(s,1H),7.07(d,J=8.1Hz,2H),6.96(d,J=7.8Hz,2H),3.57(s,3H),3.29(t,J=4.9Hz,1H),2.27(s,6H),2.26(s,3H). 13 C NMR(100MHz,CDCl3)δ178.4,144.7,141.2,139.7,134.9,133.6,128.3,128.0,50.9,21.0,18.3.HRMS(ESI)m / z:calcd for C 17 H 22 BNNaO2 + [M+Na] + 306.1636,found306.1642.

[0133] Example 35

[0134]

[0135] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 4-benzyloxyphenylacetate diazo (a26) to obtain product L32, a white solid, with a yield of 77%. 1 H NMR(400MHz,(CD3)2SO)δ8.00(s,2H),7.84(s,1H),7.43–7.36(m,4H),7.33–7.29(m,1H),7.08–7.04(m,2H),6.80–6.77(m,2H),5.02(s,2H),3.35(s,3H),3.15(t,J=4.4Hz,1H),2.27(s,6H). 13 CNMR(100MHz,(CD3)2SO)δ177.5,155.4,144.1,141.9,137.5,135.3,135.1,129.0,128.4,127.7,127.6,113.8,69.0,50.2,17.6.HRMS(ESI)m / z:calcd for C 23 H 26 BNNaO3 + [M+Na] + 398.1898,found 398.1904

[0136] Example 36

[0137]

[0138] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 4-tert-butylphenylacetate diazo (a27) to obtain product L33, a white solid, with a yield of 77%. 1 H NMR(400MHz,(CD3)2SO)δ7.94(s,2H),7.84(s,1H),7.14(dd,J=6.4Hz,1.7Hz,2H),7.05(dd,J=6.6Hz,2.0Hz,2H),3.36(s,3H),3.15(t,J=5.0Hz,1H),2.26(s,6H),1.23(s,9H). 13 C NMR(100MHz,(CD3)2SO)δ177.2,146.3,144.2,141.9,139.7,135.2,127.7,124.0,50.2,33.9,31.3,17.5.HRMS(ESI)m / z:calcd for C 20 H 28 BNNaO2 + [M+Na] + 348.2105,found348.2108.

[0139] Example 37

[0140]

[0141] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl 1-naphthylacetate diazo (a28) to obtain product L34, a pale yellow solid, with a yield of 62%. 1 H NMR(400MHz,CDCl3)δ8.11–8.08(m,1H),7.80–7.77(m,1H),7.75(s,2H),7.62(d,J=7.3Hz,1H),7.59(d,J=8.2Hz,1H),7.42–7.37(m,3H),7.31(t,J=7.7Hz,1H),4.22(t,J=4.4Hz,1H),3.61(s,3H),2.19(s,6H). 13 C NMR(100MHz,CDCl3)δ178.6,144.9,141.2,138.5,134.7,133.9,131.7,128.6,125.3,125.1,125.1,124.9,123.8,51.1,18.2.HRMS(ESI)m / z:calcd for C 20 H22 BNNaO2 + [M+Na] + 342.1636, found 342.1646.

[0142] Example 38

[0143]

[0144] Under the same conditions as in Example 1, methyl phenylacetate diazo was replaced with methyl pyridine-3-acetate diazo (a29) to obtain product L35, a pale yellow solid, with a yield of 44%. 1 H NMR(400MHz,CDCl3)δ8.29(s,1H),8.16(s,1H),7.88 - 7.85(m,3H),7.56(s,1H),7.18(dd,J=8.0,4.8Hz,1H),3.57(s,3H),3.30(t,J=5.2Hz,1H),2.30(s,6H). 13 C NMR(100MHz,CDCl3)δ177.5,148.7,145.6,144.5,141.9,135.6,123.3,51.1,18.4.HRMS(ESI)m / z:calcd for C 15 H 20 BN2O2 + [M+H] + 271.1613, found 271.1619.

Claims

1. A method for the visible light-catalyzed synthesis of organic boron compounds, characterized in that, Under the action of visible light, an aryl diazoacetate and an amino borane adduct react to obtain an organoboron compound; ; wherein R 1 is a nitrogen heterocycle; R 2 is any one of aryl, heteroaryl, substituted aryl and substituted heteroaryl; R 3 is any one of alkyl, aryl, substituted aryl, allyl; the organic solvent is one or a combination of more of dichloromethane, 1,2-dichloroethane, ethyl acetate and chloroform; The substituents in the substituted aryl and the substituted heteroaryl are each independently selected from at least one of fluorine, chlorine, bromine, cyano, alkyl, aryl, haloalkyl, alkoxy, and aryloxy.

2. The method for visible-light catalytic synthesis of an organoboron compound according to claim 1, wherein, The azacycle is any one of an azaaryl and a substituted azaaryl; the aryl is phenyl or naphthyl; the heteroaryl is pyridyl, thienyl, piperidyl, or pyrrolyl; The substituents in the substituted azaaryl are each independently selected from at least one of alkyl, fluorine, chlorine, and haloalkyl.

3. The method for visible light catalytic synthesis of organoboron compounds according to claim 1, characterized in that, Dissolve the aryl diazoacetate and the amino borane adduct in an organic solvent, mix and react under the irradiation of visible light, and separate and purify after the reaction to obtain the organoboron compound.

4. The method for visible-light catalytic synthesis of organic boron compounds according to claim 3, wherein, The molar ratio of the aryl diazoacetate to the amino borane adduct is 1:2 to 1:

6.

5. The method for visible-light catalytic synthesis of organic boron compounds according to claim 3, wherein The concentration of the aryl diazoacetate is 0.05 to 0.4 moL / L.

6. The method for visible light-catalyzed synthesis of an organoboron compound according to claim 3, wherein The reaction time is 5 to 24 hours; the reaction temperature is room temperature.

7. The method for photocatalytic synthesis of organic boron compounds according to claim 1, characterized in that, The wavelength of the visible light is 450 to 500 nanometers.

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