A method for stereodispersive synthesis of iodoallyl compounds

Abstract

This invention relates to the field of organic chemical synthesis, specifically to a method for the stereodispersive synthesis of iodoallyl compounds, including E-type and Z-type iodoallyl compounds. This invention provides a novel stereodispersive method for the synthesis of iodoallyl compounds, which has broad substrate applicability and can prepare a variety of iodoallyl compounds. Furthermore, in the presence of a photocatalyst or a manganese catalyst and a base, high temperature and high pressure are not required; iodoallyl compounds can be prepared stereodispersively simply by visible light irradiation. In other words, the reaction conditions of this invention are mild and the operation is simple. The method also has broad substrate applicability and can prepare a variety of iodoallyl compounds. By using specific starting materials, which do not require any further treatment or modification and can be used directly in the reaction, the reaction steps are few and the process is simple, showing broad application prospects.

Description

Technical Field

[0001] This invention relates to the field of organic chemical synthesis, and more particularly to a method for the stereodispersive synthesis of iodoallyl compounds. Background Technology

[0002] Allyl halogens are important building blocks in organic synthesis, possessing two convertible functional groups (halogen and allylic functional groups) that can be used for subsequent synthetic transformations. Currently, there are numerous reported methods for synthesizing allyl halogens, most of which involve atom-transfer radical addition reactions between alkynes and α-functionalized haloalkanes initiated by free radical initiators or metal reagents. The shortcomings of the reported atom-transfer radical addition reactions between alkynes and α-functionalized haloalkanes are: (1) the stereoselectivity of the resulting allyl halogens is difficult to control, making it difficult to achieve stereospecific synthesis of E or Z isomers; (2) the free radical initiators used in these methods, such as tributyltin hydrogen, are highly toxic, and triethylboron is flammable; (3) most α-functionalized haloalkanes are highly reactive halogens such as perfluoroalkanes.

[0003] In summary, the synthesis of iodoallyl compounds has attracted considerable attention, and numerous strategies have been developed to synthesize various iodoallyl compounds. However, these methods have some drawbacks, such as the relatively hazardous reagents, poor substrate universality, difficulty in synthesizing iodoallyl compounds with high stereoselectivity, and the inability to achieve stereodispersive synthesis of iodoallyl compounds. For example, patent document CN103254029A discloses a method for synthesizing 2-iodoallyl fluorine compounds, which synthesizes E-type 2-iodoallyl fluorine compounds through the iodination reaction of simple allenes, N-iodosuccinimide, and triethylamine trihydrofluoride. However, its reagents are relatively hazardous, and its substrate universality is poor. Therefore, based on the aforementioned related technologies, there is an urgent need to develop a stereodispersive method for synthesizing iodoallyl compounds. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide a stereodispersive method for the synthesis of iodoallyl compounds, in order to solve the problems of dangerous reaction reagents and low stereoselectivity of products in the prior art.

[0005] To achieve the above objectives, the present invention provides a method for the stereodispersive synthesis of iodoallyl compounds.

[0006] A method for stereodispersive synthesis of iodoallyl compounds, wherein the stereodispersive synthesis of iodoallyl compounds includes E-type iodoallyl compounds and Z-type iodoallyl compounds;

[0007] The E-type iodoallyl compound was prepared from raw material A, raw material B, organic solvent, photocatalyst, and alkali.

[0008] The Z-type iodoallyl compound was prepared from raw material A, raw material B, organic solvent, manganese catalyst, and base.

[0009] The structural formula of raw material A is as follows:

[0010]

[0011] The structural formula of raw material B is as follows:

[0012]

[0013] The R 1 It is aryl; R 2 It is hydrogen; R 3 It can be any one of cyano, trifluoromethyl, difluoromethyl, ester, and amide groups.

[0014] Preferably, the organic solvent is any one of dichloroethane, toluene, and acetonitrile.

[0015] Preferably, the photocatalyst is any one of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile, bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium di(hexafluorophosphate) and (OC-6-22)-tris[2-(2,4-difluorophenyl)pyridine]iridium(III).

[0016] Preferably, the base is any one of 1,2,2,6,6-pentamethylpiperidine, potassium phosphate, sodium carbonate, sodium phosphate, and cesium carbonate.

[0017] Preferably, the manganese catalyst is decacarbonyldimanganese.

[0018] Preferably, the method for preparing the E-type iodoallyl compound is as follows:

[0019] Step A1: Add the photocatalyst and base to the reaction tube in sequence, then place it in a glove box. Add the organic solvent, raw material A and raw material B to the glove box, stir for 25-30 minutes, seal the reaction tube, and obtain the reaction solution.

[0020] Step A2: Remove the reaction solution from the glove box, react it under irradiation at room temperature (420-430 nm) for 35-45 hours, and then evaporate it to dryness to obtain the E-type iodoallyl compound.

[0021] Preferably, the ratio of photocatalyst, alkali, organic solvent, raw material A and raw material B in step A1 is 0.02-0.05g: 0.5-1g: 10-30mL: 0.5-1.2g: 2-3g.

[0022] Preferably, the preparation method of the Z-type iodoallyl compound is as follows:

[0023] Step B1: Add alkali to the reaction tube, then place it in a glove box. In the glove box, add manganese catalyst, organic solvent, raw material A and raw material B in sequence, stir for 25-30 minutes, seal the reaction tube, and obtain the reaction solution.

[0024] Step B2: Remove the reaction solution from the glove box, and allow it to react for 2-5 hours under irradiation at room temperature (450-460 nm). Then, evaporate the solution to dryness to obtain the Z-type iodoallyl compound.

[0025] Preferably, the ratio of the amount of alkali, manganese catalyst, organic solvent, raw material A and raw material B in step B1 is 1.8-2.2g: 0.1-0.3g: 10-30mL: 1-3g: 0.5-2g.

[0026] The beneficial effects of this invention are:

[0027] This invention provides a novel stereodispersive method for the synthesis of iodoallyl compounds. The method has broad substrate applicability and can prepare a variety of iodoallyl compounds. Furthermore, in the presence of a photocatalyst or a manganese catalyst and a base, iodoallyl compounds can be prepared stereodispersively without high temperature or high pressure; only visible light irradiation is required. Therefore, the reaction conditions of this invention are mild and the operation is simple. The method also utilizes specific starting materials that do not require any further treatment or modification and can be used directly in the reaction. The process involves few steps and is simple, showing broad application prospects. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only for this invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 This is a reaction mechanism diagram of the E-type iodoallyl compound and the Z-type iodoallyl compound in this invention. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments.

[0031] The sources and properties of some of the raw materials used in this invention are as follows:

[0032] 2,4,5,6-Tetra(9-carbazolyl)-isophthalonitrile was purchased from Zhengzhou Alpha Chemical Co., Ltd.; bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium di(hexafluorophosphate) was purchased from Shanghai Haohong Biomedical Technology Co., Ltd.; (OC-6-22)-tris[2-(2,4-difluorophenyl)pyridine]iridium(III) was purchased from Zhengzhou Huiju Chemical Co., Ltd.; decacarbonyldimanganese was purchased from Shanghai Jieshikai Biotechnology Co., Ltd.

[0033] Example 1: A method for stereodispersive synthesis of iodoallyl compounds, comprising the following steps:

[0034] S1: Add 0.02g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 0.5g of potassium phosphate to the reaction tube in sequence, then place it in a glove box, add 10mL of toluene, 0.5g of phenylacetylene and 2g of iodoacetonitrile to the glove box, stir for 25min, seal the reaction tube, and obtain the reaction solution.

[0035] S2: Remove the reaction solution from the glove box, react it under 420 nm irradiation at room temperature for 35 h, and then evaporate to dryness to obtain the E-type iodoallyl compound, with the following structural formula:

[0036]

[0037] S3: Add 1.8g of sodium carbonate to the reaction tube, then place it in a glove box. In the glove box, add 0.1g of decacarbonyl dimanganese, 10mL of toluene, 1g of phenylacetylene and 0.5g of iodoacetonitrile in sequence, stir for 25min, seal the reaction tube, and obtain the reaction solution.

[0038] S4: Remove the reaction solution from the glove box, react it at room temperature under 450 nm irradiation for 2 hours, and then evaporate to dryness to obtain the Z-type iodoallyl compound with the following structural formula:

[0039]

[0040] Example 2: A method for stereodispersive synthesis of iodoallyl compounds, comprising the following steps:

[0041] S1: Add 0.03g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 0.6g of cesium carbonate to the reaction tube in sequence, then place it in a glove box. Add 12mL of toluene, 0.6g of 4-bromo-phenylacetylene and 2.1g of iodoacetonitrile to the glove box, stir for 26min, seal the reaction tube, and obtain the reaction solution;

[0042] S2: The reaction solution was removed from the glove box and reacted under 422 nm irradiation at room temperature for 36 h, followed by rotary evaporation to obtain the E-type iodoallyl compound, with the following structural formula:

[0043]

[0044] S3: Add 1.9g of sodium carbonate to the reaction tube, then place it in a glove box. In the glove box, add 0.15g of decacarbonyldimanganese, 12mL of toluene, 1.2g of 4-bromo-phenylacetylene and 0.8g of iodoacetonitrile in sequence, stir for 26min, seal the reaction tube, and obtain the reaction solution.

[0045] S4: Remove the reaction solution from the glove box and react it under 452 nm irradiation at room temperature for 2-5 hours, then evaporate to dryness to obtain the Z-type iodoallyl compound, with the following structural formula:

[0046]

[0047] Example 3: A method for stereodispersive synthesis of iodoallyl compounds, comprising the following steps:

[0048] S1: Add 0.04g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 0.7g of potassium phosphate to the reaction tube in sequence, then place it in a glove box. Add 14mL of toluene, 0.7g of 4-chloro-phenylacetylene and 2.3g of iodoacetonitrile to the glove box, stir for 27min, seal the reaction tube, and obtain the reaction solution.

[0049] S2: The reaction solution was removed from the glove box and reacted under 424 nm irradiation at room temperature for 37 h, followed by rotary evaporation to obtain the E-type iodoallyl compound, with the following structural formula:

[0050]

[0051] S3: Add 2g of sodium carbonate to the reaction tube, then place it in a glove box. In the glove box, add 0.18g of decacarbonyldimanganese, 14mL of toluene, 1.5g of 4-chloro-phenylacetylene and 0.8g of iodoacetonitrile in sequence, stir for 28min, seal the reaction tube, and obtain the reaction solution.

[0052] S4: Remove the reaction solution from the glove box, react it at room temperature under 455 nm irradiation for 3 hours, and then evaporate to dryness to obtain the Z-type iodoallyl compound with the following structural formula:

[0053]

[0054] Example 4: A method for stereodispersive synthesis of iodoallyl compounds, comprising the following steps:

[0055] S1: Add 0.03g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 0.8g of potassium phosphate to the reaction tube in sequence, then place it in a glove box. Add 18mL of toluene, 0.8g of 4-methoxy-phenylacetylene and 2.5g of iodoacetonitrile to the glove box, stir for 27min, seal the reaction tube, and obtain the reaction solution.

[0056] S2: The reaction solution was removed from the glove box and reacted under 425 nm irradiation at room temperature for 38 h, followed by rotary evaporation to obtain the E-type iodoallyl compound, with the following structural formula:

[0057]

[0058] S3: Add 2.1g of sodium carbonate to the reaction tube, then place it in a glove box. In the glove box, add 0.2g of decacarbonyldimanganese, 18mL of toluene, 1.8g of 4-methoxy-phenylacetylene and 0.8g of iodoacetonitrile in sequence, stir for 27min, seal the reaction tube, and obtain the reaction solution.

[0059] S4: Remove the reaction solution from the glove box, react it at room temperature under 458 nm irradiation for 3 hours, and then evaporate to dryness to obtain the Z-type iodoallyl compound with the following structural formula:

[0060]

[0061] Example 5: A method for stereodispersive synthesis of iodoallyl compounds, comprising the following steps:

[0062] S1: Add 0.04g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 0.8g of cesium carbonate to the reaction tube in sequence, then place it in a glove box. Add 20mL of toluene, 1g of 3-bromo-phenylacetylene and 2.5g of iodoacetonitrile to the glove box, stir for 28min, seal the reaction tube, and obtain the reaction solution;

[0063] S2: The reaction solution was removed from the glove box and reacted under 428 nm irradiation at room temperature for 40 h, followed by rotary evaporation to obtain the E-type iodoallyl compound, with the following structural formula:

[0064]

[0065] S3: Add 2g of sodium carbonate to the reaction tube, then place it in a glove box. In the glove box, add 0.2g of decacarbonyldimanganese, 22mL of toluene, 2.4g of 3-bromo-phenylacetylene and 1.2g of iodoacetonitrile in sequence, stir for 28min, seal the reaction tube, and obtain the reaction solution.

[0066] S4: Remove the reaction solution from the glove box, react it at room temperature under 458 nm irradiation for 4 hours, and then evaporate to dryness to obtain the Z-type iodoallyl compound with the following structural formula:

[0067]

[0068] Example 6: A method for stereodispersive synthesis of iodoallyl compounds, comprising the following steps:

[0069] S1: Add 0.04g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 0.9g of potassium phosphate to the reaction tube in sequence, then place it in a glove box. Add 28mL of toluene, 1.1g of 2-methoxy-phenylacetylene and 2.8g of iodoacetonitrile to the glove box, stir for 29min, seal the reaction tube, and obtain the reaction solution.

[0070] S2: The reaction solution was removed from the glove box and reacted under 428 nm irradiation at room temperature for 42 h, followed by rotary evaporation to obtain the E-type iodoallyl compound, with the following structural formula:

[0071]

[0072] S3: Add 2.1g of sodium carbonate to the reaction tube, then place it in a glove box. In the glove box, add 0.2g of decacarbonyldimanganese, 29mL of toluene, 2.8g of 2-methoxy-phenylacetylene and 1.8g of iodoacetonitrile in sequence, stir for 29min, seal the reaction tube, and obtain the reaction solution.

[0073] S4: Remove the reaction solution from the glove box, react it at room temperature under 458 nm irradiation for 4 hours, and then evaporate to dryness to obtain the Z-type iodoallyl compound with the following structural formula:

[0074]

[0075] Example 7: A method for stereodispersive synthesis of iodoallyl compounds, comprising the following steps:

[0076] S1: Add 0.05g of bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium di(hexafluorophosphate) salt and 1g of 1,2,2,6,6-pentamethylpiperidine to the reaction tube in sequence, then place it in a glove box, add 30mL of dichloroethane, 1.2g of phenylacetylene and 3g of α-iododifluoroethane to the glove box, stir for 30min, seal the reaction tube, and obtain the reaction solution;

[0077] S2: The reaction solution was removed from the glove box and reacted under 430 nm irradiation at room temperature for 45 h, followed by rotary evaporation to obtain the E-type iodoallyl compound, with the following structural formula:

[0078]

[0079] S3: Add 2.2g of sodium phosphate to the reaction tube, then place it in a glove box. In the glove box, add 0.3g of decacarbonyl dimanganese, 30mL of toluene, 3g of phenylacetylene and 2g of α-iododifluoroethane in sequence, stir for 30min, seal the reaction tube, and obtain the reaction solution.

[0080] S4: Remove the reaction solution from the glove box, react it at room temperature under 460 nm irradiation for 5 h, and then evaporate to dryness to obtain the Z-type iodoallyl compound, with the following structural formula:

[0081]

[0082] Example 8: A method for stereodispersive synthesis of iodoallyl compounds, comprising the following steps:

[0083] S1: Add 0.05g of bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium di(hexafluorophosphate) salt and 1g of 1,2,2,6,6-pentamethylpiperidine to the reaction tube in sequence, then place it in a glove box, add 30mL of acetonitrile, 1.2g of phenylacetylene and 3g of N,N-dimethyl-α-iodoacetamide to the glove box, stir for 30min, seal the reaction tube, and obtain the reaction solution;

[0084] S2: The reaction solution was removed from the glove box and reacted under 430 nm irradiation at room temperature for 45 h, followed by rotary evaporation to obtain the E-type iodoallyl compound, with the following structural formula:

[0085]

[0086] S3: Add 2.2g of cesium carbonate to the reaction tube, then place it in a glove box. In the glove box, add 0.3g of decacarbonyl dimanganese, 30mL of toluene, 3g of phenylacetylene and 2g of N,N-dimethyl-α-iodoacetamide in sequence, stir for 30min, seal the reaction tube, and obtain the reaction solution.

[0087] S4: Remove the reaction solution from the glove box, react it at room temperature under 460 nm irradiation for 5 h, and then evaporate to dryness to obtain the Z-type iodoallyl compound, with the following structural formula:

[0088]

[0089] Example 9: A method for stereodispersive synthesis of iodoallyl compounds, comprising the following steps:

[0090] S1: Add 0.05g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 1g of 1,2,2,6,6-pentamethylpiperidine to the reaction tube in sequence, then place it in a glove box. Add 30mL of toluene, 1.2g of 4-bromo-phenylacetylene and 3g of tert-butyl α-iodoacetate to the glove box, stir for 30min, seal the reaction tube, and obtain the reaction solution.

[0091] S2: The reaction solution was removed from the glove box and reacted under 430 nm irradiation at room temperature for 45 h, followed by rotary evaporation to obtain the E-type iodoallyl compound, with the following structural formula:

[0092]

[0093] S3: Add 2.2g of cesium carbonate to the reaction tube, then place it in a glove box. In the glove box, add 0.3g of decacarbonyl dimanganese, 30mL of toluene, 3g of 4-bromo-phenylacetylene and 2g of α-iodoacetic acid tert-butyl ester in sequence, stir for 30min, seal the reaction tube, and obtain the reaction solution.

[0094] S4: Remove the reaction solution from the glove box, react it at room temperature under 460 nm irradiation for 5 h, and then evaporate to dryness to obtain the Z-type iodoallyl compound, with the following structural formula:

[0095]

[0096] Example 10: A method for stereodispersive synthesis of iodoallyl compounds, comprising the following steps:

[0097] S1: Add 0.05g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 1g of 1,2,2,6,6-pentamethylpiperidine to the reaction tube in sequence, then place it in a glove box. Add 30mL of toluene, 1.2g of 4-methoxy-phenylacetylene and 3g of tert-butyl α-iodoacetate to the glove box, stir for 30min, seal the reaction tube, and obtain the reaction solution.

[0098] S2: The reaction solution was removed from the glove box and reacted under 430 nm irradiation at room temperature for 45 h, followed by rotary evaporation to obtain the E-type iodoallyl compound, with the following structural formula:

[0099]

[0100] S3: Add 2.2g of cesium carbonate to the reaction tube, then place it in a glove box. In the glove box, add 0.3g of decacarbonyl dimanganese, 30mL of toluene, 3g of 4-methoxy-phenylacetylene and 2g of α-iodoacetic acid tert-butyl ester in sequence, stir for 30min, seal the reaction tube, and obtain the reaction solution.

[0101] S4: Remove the reaction solution from the glove box, react it at room temperature under 460 nm irradiation for 5 h, and then evaporate to dryness to obtain the Z-type iodoallyl compound, with the following structural formula:

[0102]

[0103] Example 11: A method for stereodispersive synthesis of iodoallyl compounds, comprising the following steps:

[0104] S1: Add 0.05g of bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium di(hexafluorophosphate) salt and 1g of 1,2,2,6,6-pentamethylpiperidine to the reaction tube in sequence, then place it in a glove box, add 30mL of toluene, 1.2g of 4-ethynylbenzonitrile and 3g of α-iodotrifluoroethane to the glove box, stir for 30min, seal the reaction tube, and obtain the reaction solution;

[0105] S2: The reaction solution was removed from the glove box and reacted under 430 nm irradiation at room temperature for 45 h, followed by rotary evaporation to obtain the E-type iodoallyl compound, with the following structural formula:

[0106]

[0107] S3: Add 2.2g of sodium phosphate to the reaction tube, then place it in a glove box. In the glove box, add 0.3g of decacarbonyldimanganese, 30mL of toluene, 3g of 4-ethynylbenzonitrile and 2g of α-iodotrifluoroethane in sequence, stir for 30min, seal the reaction tube, and obtain the reaction solution.

[0108] S4: Remove the reaction solution from the glove box, react it at room temperature under 460 nm irradiation for 5 h, and then evaporate to dryness to obtain the Z-type iodoallyl compound, with the following structural formula:

[0109]

[0110] Performance testing:

[0111] The E-type iodoallyl and Z-type iodoallyl compounds prepared in Examples 1-11 were subjected to nuclear magnetic resonance (NMR) and high-resolution characterization with dibromomethane as an internal standard. The NMR yield and the ratio between the E-type and Z-type iodoallyl compounds during the preparation process were also tested. The products were then purified by silica gel column chromatography, and their properties were observed. The yield and the ratio between the E-type and Z-type iodoallyl compounds during the preparation process were calculated.

[0112] Table 1 Summary of experimental data from Examples 1-11

[0113]

[0114]

[0115] Data Analysis:

[0116] As shown in Table 1, the stereodispersive synthesis of iodoallyl compounds prepared by this invention exhibits higher yields and higher stereoselectivity. This invention provides a novel method for the stereodispersive synthesis of iodoallyl compounds, which has broad substrate applicability and can prepare a variety of iodoallyl compounds. Furthermore, in the presence of a photocatalyst or a manganese catalyst and a base, high temperature and high pressure are not required; iodoallyl compounds can be prepared stereodispersively simply by visible light irradiation. Therefore, the reaction conditions of this invention are mild and the operation is simple. The method also has broad substrate applicability and can prepare a variety of iodoallyl compounds. By using specific starting materials, which do not require any further treatment or modification and can be used directly in the reaction, the reaction steps are few and the process is simple.

[0117] The E-type iodoallyl compound prepared in Example 1 was characterized by nuclear magnetic resonance, and the results are as follows:

[0118] 1H NMR(400MHz, CDCl3)δE-isomer(major)7.41-7.27(m,5H),6.46(t,J=7.5Hz,1H),2.98(d,J=7 .5Hz,2H).Z-isomer(minor)7.47-7.40(m,5H),6.01(t,J=6.5Hz,1H),3.39(d,J=6.5Hz,2H).

[0119] 13 C NMR (101MHz, CDCl3) δ140.1,129.3,128.9,128.7,128.1,116.4,101.9,20.0.

[0120] The Z-type iodoallyl compound prepared in Example 1 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0121] 1 H NMR(400MHz, CDCl3)δZ-isomer(major)7.46(d,J=3.7Hz,2H),7.33(dd,J=5.1,2.1Hz,3H),6.01(t,J=6.5Hz,1H),3. 40(d,J=6.5Hz,2H).E-isomer(minor)7.41-7.35(m,3H),7.28(s,2H),6.46(t,J=7.5Hz,1H),2.99(d,J=7.5Hz,2H).

[0122] 13 C NMR (126MHz, CDCl3) δ141.8,129.4,128.6,128.5,125.9,116.8,111.7,26.6.

[0123] EI-MS: calculated for [C 10 H8NI],268.97014; Found 268.97017.

[0124] The E-type iodoallyl compound prepared in Example 2 was characterized by nuclear magnetic resonance, and the results are as follows:

[0125] 1H NMR(400MHz, CDCl3)δE-isomer(major)7.52(d,J=8.5Hz,2H),7.15(d,J=8.4Hz,2H),6.48(t,J=7 .5Hz,1H),2.96(d,J=7.5Hz,2H).Z-isomer(minor)6.02(t,J=6.5Hz,1H),3.37(d,J=6.5Hz,2H).

[0126] 13 C NMR (101MHz, CDCl3) δ139.0,132.2,129.7,129.4,123.5,116.2,100.2,20.1.

[0127] The Z-type iodoallyl compound prepared in Example 2 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0128] 1 H NMR(400MHz, CDCl3)δZ-isomer(major)7.50-7.45(m,2H),7.35-7.29(m,2H),6.02(t,J=6.5Hz,1H),3.38(d,J=6.5Hz ,2H).E-isomer(minor)7.52(dd,J=8.4,1.6Hz,2H),7.18-7.11(m,2H),6.48(t,J=7.5Hz,1H),2.97(d,J=7.5Hz,2H).

[0129] 13 C NMR (126MHz, CDCl3) δ140.8,131.8,130.0,126.6,123.7,116.6,110.1,26.6.

[0130] EI-MS: calculated for [C 10 H7NIBr],346.88066; Found 346.88068.

[0131] The E-type iodoallyl compound prepared in Example 3 was characterized by nuclear magnetic resonance, and the results are as follows:

[0132] 1H NMR(400MHz, CDCl3)δE-isomer(major)7.36(d,J=8.5Hz,2H),7.22(d,J=8.5Hz,2H),6.47(t,J=7 .5Hz,1H),2.97(d,J=7.5Hz,2H).Z-isomer(minor)6.01(t,J=6.4Hz,1H),3.38(d,J=6.5Hz,2H).

[0133] 13 C NMR (101MHz, CDCl3) δ138.6,135.3,129.5,129.4,129.2,116.2,100.2,20.1.

[0134] The Z-type iodoallyl compound prepared in Example 3 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0135] 1 H NMR(400MHz, CDCl3)δZ-isomer(major)7.41-7.36(m,2H),7.31(d,J=8.7Hz,2H),6.01(t,J=6.5Hz,1H),3.38(d,J =6.5Hz,2H).E-isomer(minor)7.36-7.34(m,2H),7.25-7.19(m,2H),6.48(t,J=7.5Hz,1H),2.97(d,J=7.5Hz,2H).

[0136] 13 C NMR (126MHz, CDCl3) δ140.2,135.3,129.6,128.7,126.4,116.5,109.9,26.5.

[0137] EI-MS: calculated for [C 10 H7NICl],302.93117; Found 302.93116.

[0138] The E-type iodoallyl compound prepared in Example 4 was characterized by nuclear magnetic resonance, and the results are as follows:

[0139] 1H NMR(400MHz, CDCl3)δE-isomer(major)7.22(d,J=8.7Hz,2H),6.88(d,J=8.8Hz,2H),6.41(t,J=7.5Hz,1H),3.83(s,3H),2.99(d,J =7.5Hz,2H).Z-isomer(minor)7.31(d,J=8.7Hz,2H),6.94(d,J=8.8Hz,2H),5.93-5.88(m,1H),3.84(s,3H),3.11(d,J=7.7Hz,2H).

[0140] 13 C NMR (101MHz, CDCl3) δ160.1,132.4,129.7,128.2,116.6,114.2,102.3,55.5,20.1.

[0141] The Z-type iodoallyl compound prepared in Example 4 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0142] 1 H NMR(400MHz, CDCl3)δZ-isomer(major)7.44-7.35(m,2H),6.88-6.82(m,2H),5.91(t,J=6.5Hz,1H),3.83(s,3H),3.38(d,J=6.5H z,2H), E-isomer(minor)7.22(d,J=8.8Hz,2H),6.91(d,J=8.8Hz,2H),6.41(t,J=7.5Hz,1H),3.87(s,3H),2.99(d,J=7.5Hz,2H).

[0143] 13 C NMR (126MHz, CDCl3) δ160.4,134.3,129.8,124.1,116.9,113.7,111.6,55.5,26.6.

[0144] EI-MS: calculated for [C 11 H 10 NIO],298.98071; Found 298.98073.

[0145] The E-type iodoallyl compound prepared in Example 5 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0146] 1H NMR(400MHz, CDCl3)δE-isomer(major)7.47(ddd,J=7.9,2.0,1.2Hz,1H),7.41(t,J=1.8Hz,1H),7.29-7.24(m,1H),7.20(dt,J =7.7, 1.4Hz, 1H), 6.48 (t, J = 7.5Hz, 1H), 2.99 (d, J = 7.4Hz, 2H). Z-isomer (minor) 6.05 (t, J = 6.5Hz, 1H), 3.39 (d, J = 6.5Hz, 2H).

[0147] 13 C NMR (101MHz, CDCl3) δ141.9,132.3,130.9,130.4,129.7,126.6,122.7,116.0,99.1,20.0.

[0148] EI-MS: calculated for [C 10 H7BrNI],346.88011; Found 346.88017.

[0149] The Z-type iodoallyl compound prepared in Example 5 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0150] 1 H NMR (400MHz, CDCl3) δZ-isomer (major) 7.48-7.43 (m, 2H), 7.38 (dt, J = 7.9, 1.4Hz, 1H), 7.35 (s, 1H), 6.0 5(t,J=6.5Hz,1H),3.39(d,J=6.6Hz,2H).E-isomer(minor)6.48(t,J=7.5Hz,1H),2.98(d,J=7.6Hz,2H).

[0151] 13 C NMR (126MHz, CDCl3) δ143.6,133.3,132.3,131.3,130.2,130.0,127.1,120.3,109.1,26.4.

[0152] EI-MS: calculated for [C 10 H7BrNI],346.88011; Found 346.88015.

[0153] The E-type iodoallyl compound prepared in Example 6 was characterized by nuclear magnetic resonance, and the results are as follows:

[0154] 1 H NMR(400MHz, CDCl3)δE-isomer(major)7.40-7.29(m,1H),7.20(dd,J=7.6,1.7Hz,1H),6.98(t,J=7.5Hz,1H),6.89(d,J=8.3Hz,1H),6 .46(t,J=7.3Hz,1H),3.88(s,3H),2.85(d,J=7.2Hz,2H).Z-isomer(minor)5.84(t,J=6.4Hz,1H),3.86(s,3H),3.37(d,J=6.4Hz,2H).

[0155] 13 C NMR (101MHz, CDCl3) δ155.1,130.8,130.1,128.2,120.9,116.5,111.4,96.5,55.6,20.1.

[0156] The Z-type iodoallyl compound prepared in Example 6 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0157] 1 H NMR(400MHz,CDCl3)δZ-isomer 7.34-7.27(m,1H),7.18(dd,J=7.5,1.8Hz,1H),6.93(td,J=7.5,1.1Hz,1H), 6.90-6.85(m,1H),5.84(t,J=6.4Hz,1H),3.86(s,3H),3.37(d,J=6.4Hz,2H).

[0158] 13 C NMR (101MHz, CDCl3) δ156.2,130.6,130.2,127.7,120.5,111.4,55.7,26.2.

[0159] EI-MS: calculated for [C 11 H 10 NIO],298.98071; Found 298.98073.

[0160] The E-type iodoallyl compound prepared in Example 7 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0161] 1H NMR(400MHz, CDCl3)δE-isomer(major)7.40-7.27(m,5H),6.50(t,J=7.6Hz,1H),5.77(tt,J=56.3,4.2Hz,1H),2 .52(tdd,J=17.3,7.6,4.2Hz,2H).Z-isomer(minor)7.51-7.41(m,5H),5.99(t,J=5.6Hz,1H),3.07-2.83(m,2H).

[0162] 13 C NMR (126MHz, CDCl3)δ 13 C NMR (126MHz, CDCl3) δ 141.1, 132.1 (t, J = 6.4Hz), 128.6, 128.5, 128.3, 114.9 (t, J = 241.3Hz), 100.3, 36.7 (t, J = 22.2Hz).

[0163] 19 F NMR (376MHz, CDCl3) δZ-isomer (minor)-115.21 (dt, J = 56.3, 17.3Hz). E-isomer (major) - 115.93 (dt, J = 56.4, 17.4Hz).

[0164] EI-MS: calculated for [C 10 H9F2I],293.97115; Found 293.97148.

[0165] The Z-type iodoallyl compound prepared in Example 7 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0166] 1 H NMR(400MHz, CDCl3)δZ-isomer(major)7.49-7.44(m,2H),7.36-7.27(m,3H),6.10-5.82(t,t,t,J=4.3,4.4,4.3Hz,1H),5.98(t ,J=6.8Hz,1H),2.91(tdd,J=17.4,6.7,4.3Hz,2H).E-isomer(minor)6.50(t,J=7.6Hz,1H),2.52(tdd,J=17.3,7.6,4.2Hz,2H).

[0167] 13 C NMR (126MHz, CDCl3)δ 13C NMR (101MHz, CDCl3) δ142.8, 128.9, 128.6, 128.5, 128.5, 115.4 (t, J = 241.2Hz), 110.3, 42.9 (t, J = 22.2Hz).

[0168] 19 F NMR (376MHz, CDCl3) δZ-isomer (major)-115.22 (dt, J = 56.0, 17.2Hz), E-isomer (minor) - 115.93 (dt, J = 56.5, 17.5Hz).

[0169] EI-MS: calculated for [C 10 H9F2I],293.97115; Found 293.97151.

[0170] The E-type iodoallyl compound prepared in Example 8 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0171] 1 H NMR(400MHz, CDCl3)δE-isomer(major)7.36-7.28(m,5H),6.69(t,J=7.3Hz,1H),3.02(d,J=7.3Hz,2H),2.91(s,3H),2. 80(s,3H).Z-isomer(minor)7.56-7.45(m,5H),6.33(t,J=6.1Hz,1H),3.38(d,J=6.1Hz,2H),3.08(s,3H),2.98(s,3H).

[0172] 13 C NMR (101MHz, CDCl3) δ169.6,141.5,135.6,128.7,128.5,97.2,36.4.

[0173] ESI-MS: calculated for C 12 H 14 INONa[M+Na] + ,338.0012;Found 338.0015.

[0174] The Z-type iodoallyl compound prepared in Example 8 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0175] 1H NMR(400MHz, CDCl3)δZ-isomer(major)7.52-7.45(m,2H),7.33-7.27(m,3H),6.33(t,J=6.2Hz,1H),3.38(d,J=6.2Hz,2 H),3.09(s,3H),2.99(s,3H).E-isomer(minor)6.70(t,J=7.3Hz,1H),3.03(d,J=7.3Hz,2H),2.91(s,3H),2.80(s,3H).

[0176] 13 C NMR (126MHz, CDCl3) δ170.0,142.7,135.7,132.6,128.8,128.6,128.3,107.3,43.0,37.6,35.8.

[0177] ESI-MS: calculated for C 12 H 14 INONa[M+Na] + ,338.0012;Found 338.0016.

[0178] The E-type iodoallyl compound prepared in Example 9 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0179] 1 H NMR(500MHz, CDCl3)δE-isomer(major)7.46(d,J=8.5Hz,2H),7.17(d,J=8.5Hz,2H),6.64(t,J=7.6Hz,1H),2.88(d,J=7.5Hz,2H),1. 44(s,9H).Z-isomer(minor)7.43(d,J=8.6Hz,2H),7.34(d,J=8.6Hz,2H),6.21(t,J=6.3Hz,1H),3.26(d,J=6.4Hz,2H),1.48(s,9H).

[0180] 13 C NMR (126MHz, CDCl3) δ169.2,140.3,135.5,131.0,122.6,96.2,81.6,38.5,28.2.

[0181] ESI-MS: calculated for C 14 H 16 BrIO₂Na[M+Na] +,444.9271;Found 444.9264.

[0182] The Z-type iodoallyl compound prepared in Example 9 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0183] 1 H NMR (400MHz, CDCl3) δZ-isomer (major) 7.43 (d, J = 8.6 Hz, 2H), 7.34 (d, J = 8.5 Hz, 2H), 6.21 (t, J = 6. 3Hz, 1H), 3.26 (d, J = 6.3Hz, 2H), 1.48 (s, 9H). E-isomer (minor) 2.88 (d, J = 7.5Hz, 2H), 1.44 (s, 9H).

[0184] 13 C NMR (101MHz, CDCl3) δ169.8,141.8,132.2,131.4,130.2,122.7,105.9,81.6,44.3,28.3.

[0185] ESI-MS: calculated for C 14 H 16 BrIO₂Na[M+Na] + ,444.9271;Found 444.9266.

[0186] The E-type iodoallyl compound prepared in Example 10 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0187] 1 H NMR(400MHz, CDCl3)δE-isomer(major)7.24(d,J=8.8Hz,2H),6.84(d,J=8.7Hz,2H),6.6(t,J=7.5Hz,1H),3.81(s,3H),2.91(d,J=7.5Hz,2H),1. 44(s,9H).Z-isomer(minor)7.42(d,J=8.8Hz,2H),6.81(s,2H),6.59(t,J=7.5Hz,1H),6.10(t,J=6.4Hz,1H),3.26(d,J=6.3Hz,2H),1.48(s,9H).

[0188] 13C NMR (126MHz, CDCl3) δ169.6,159.5,134.3,130.2,113.7,98.4,81.3,55.5,38.5,28.2.

[0189] ESI-MS: calculated for C 15 H 19 IO3Na[M+Na] + ,397.0271;Found397.0270.

[0190] The Z-type iodoallyl compound prepared in Example 10 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0191] 1 H NMR(400MHz, CDCl3)δZ-isomer(major)7.42(d,J=8.8Hz,2H),6.82(d,J=8.8Hz,2H),6.10(t,J=6.4Hz,1H),3.81(s,3H),3.27(d,J=6.4Hz, 2H), 1.48 (s, 9H). E-isomer (minor) 7.23 (d, J = 8.4Hz, 2H), 6.88 (d, J = 8.7Hz, 2H), 6.58 (t, J = 7.6Hz, 1H), 2.91 (d, J = 7.5Hz, 2H), 1.44 (s, 9H).

[0192] 13 C NMR (101MHz, CDCl3) δ170.1,159.9,135.6,129.9,122.5,113.6,107.5,81.4,55.5,44.4,28.3.

[0193] ESI-MS: calculated for C 15 H 19 IO3Na[M+Na] + ,397.0271;Found397.0274.

[0194] The E-type iodoallyl compound prepared in Example 11 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0195] 1H NMR(400MHz, CDCl3)δE-isomer(major)7.67(d,J=8.5Hz,2H),7.37(d,J=8.4Hz,2H),6.56(t,J=7.7Hz,1H),2.70(qd,J=10.3,7 .7Hz,2H).Z-isomer(minor)7.63(d,J=8.4Hz,2H),7.56(d,J=8.5Hz,2H),6.09(t,J=6.6Hz,1H),3.18(qd,J=10.6,6.6Hz,2H).

[0196] 13 C NMR (101MHz, CDCl3) δ145.3, 132.6, 131.7 (q, J = 3.3Hz), 129.1, 125.0 (q, J = 277.3Hz), 118.2, 112.8, 98.7, 36.6 (q, J = 30.2Hz).

[0197] 19 F NMR(376MHz, CDCl3)δZ-isomer(minor)-65.06.E-isomer(major)-65.61.

[0198] EI-MS: calculated for [C 11 H7NF3I],336.95698; Found 336.95680.

[0199] The Z-type iodoallyl compound prepared in Example 11 was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows:

[0200] 1 H NMR(400MHz, CDCl3)δZ-isomer(major)7.63(d,J=8.5Hz,2H),7.59-7.54(m,2H),76.09(t,J=6.6Hz,1H),3.18(qd,J=10.6, 6.6Hz,2H).E-isomer(minor)7.67(dd,J=8.4,2.0Hz,2H),7.37(d,J=8.3Hz,2H),6.56(t,J=7.7Hz,1H),2.78-2.61(m,2H).

[0201] 13C NMR (101MHz, CDCl3) δ146.6, 132.4, 129.5 (q, J = 3.9Hz), 125.6 (q, J = 277.6Hz), 129.3, 118.3, 112.8, 108.3, 42.9 (q, J = 30.0Hz).

[0202] 19 F NMR (376MHz, CDCl3) δZ-isomer (major)-65.04 (t, J = 10.6Hz). E-isomer (minor) - 65.59 (t, J = 10.3Hz).

[0203] EI-MS: calculated for [C 11 H7NF3I],336.95698; Found 336.95689.

[0204] Those skilled in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the invention is limited to these examples; within the framework of the invention, the technical features of the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.

[0205] This invention is intended to cover all such substitutions, modifications, and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this invention should be included within the scope of protection of this invention.

Claims

1. A method for stereodispersive synthesis of iodoallyl compounds, characterized in that, The stereodispersive synthesis of iodoallyl compounds includes E-type iodoallyl compounds and Z-type iodoallyl compounds; The E-type iodoallyl compound was prepared from raw material A, raw material B, organic solvent, photocatalyst, and alkali. The preparation method of the E-type iodoallyl compound is as follows: Step A1: Add the photocatalyst and base to the reaction tube in sequence, then place it in a glove box. Add the organic solvent, raw material A and raw material B to the glove box, stir for 25-30 minutes, seal the reaction tube, and obtain the reaction solution. Step A2: Remove the reaction solution from the glove box, react it under irradiation at room temperature (420-430 nm) for 35-45 hours, and then evaporate it to dryness to obtain the E-type iodoallyl compound. The photocatalyst is any one of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile, bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium di(hexafluorophosphate) and (OC-6-22)-tris[2-(2,4-difluorophenyl)pyridine]iridium(III); The Z-type iodoallyl compound was prepared from raw material A, raw material B, organic solvent, manganese catalyst, and base. The preparation method of the Z-type iodoallyl compound is as follows: Step B1: Add alkali to the reaction tube, then place it in a glove box. In the glove box, add manganese catalyst, organic solvent, raw material A and raw material B in sequence, stir for 25-30 minutes, seal the reaction tube, and obtain the reaction solution. Step B2: Remove the reaction solution from the glove box, react the reaction solution under irradiation at room temperature (450-460 nm) for 2-5 hours, and then evaporate to dryness to obtain the Z-type iodoallyl compound; The manganese catalyst is decacarbonyldimanganese; The structural formula of raw material A is as follows: ； The structural formula of raw material B is as follows: ； The R 1 It is aryl; R 2 It is hydrogen; R 3 It can be any one of cyano, trifluoromethyl, difluoromethyl, ester, and amide groups.

2. The method for stereodispersive synthesis of iodoallyl compounds according to claim 1, characterized in that, The organic solvent is any one of dichloroethane, toluene, and acetonitrile.

3. The method for stereodispersive synthesis of iodoallyl compounds according to claim 1, characterized in that, The base is any one of 1,2,2,6,6-pentamethylpiperidine, potassium phosphate, sodium carbonate, sodium phosphate, and cesium carbonate.

4. The method for stereodispersive synthesis of iodoallyl compounds according to claim 1, characterized in that, The ratio of photocatalyst, alkali, organic solvent, raw material A and raw material B used in step A1 is 0.02-0.05g: 0.5-1g: 10-30mL: 0.5-1.2g: 2-3g.

5. The method for stereodispersive synthesis of iodoallyl compounds according to claim 1, characterized in that, The ratio of the amount of alkali, manganese catalyst, organic solvent, raw material A and raw material B used in step B1 is 1.8-2.2g: 0.1-0.3g: 10-30mL: 1-3g: 0.5-2g.

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