Method for stereodivergently synthesizing iodo-allyl compound

Abstract

The invention relates to the field of organic chemical synthesis, in particular to a method for stereodivergently synthesizing an iodo-allyl compound, which comprises an E-type iodo-allyl compound and a Z-type iodo-allyl compound. The invention provides a novel method for stereodivergently synthesizing the iodo-allyl compound, and the method is wide in substrate applicability and can be used for preparing various iodo-allyl compounds; meanwhile, in the presence of a photocatalyst or a manganese catalyst and alkali, the iodo-allyl compound can be prepared in a three-dimensional divergent manner only through visible light irradiation without high temperature and high pressure, that is, the reaction condition is mild, and the operation is simple; meanwhile, the method is wide in substrate applicability and can be used for preparing various iodo-allyl compounds. The specific initial raw materials are adopted, the initial raw materials do not need to be subjected to any other treatment and modification and can be directly used for the reaction, the reaction steps are few, the process is simple, and wide application prospects are achieved.

Description

Technical Field

[0001] The invention relates to the field of organic chemical synthesis, and in particular to a method for synthesizing iodine allyl compounds in a stereo-divergent manner. Background Art

[0002] Haloallyl compounds are important building blocks for organic synthesis. They have two convertible functional groups (halogen and allylic functional groups) that can be used for subsequent synthetic transformations. Currently, there are many reports on the methods for synthesizing haloallyl compounds. Most of them are constructed by atom transfer radical addition reactions between alkynes and α-functionalized halogenated hydrocarbons initiated by free radical initiators or metal reagents. The shortcomings of the atom transfer radical addition reactions between alkynes and α-functionalized halogenated hydrocarbons reported at home and abroad are: (1) The stereoselectivity of the haloallyl compounds obtained is difficult to control, and it is 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) α-functionalized halogenated hydrocarbons are mostly highly active halogenated hydrocarbons such as perfluorohaloalkanes.

[0003] In summary, the synthesis of iodoallyl compounds has attracted much attention, and there are many strategies to achieve the synthesis of a variety of iodoallyl compounds. However, these methods have some defects, such as most of the reaction reagents are dangerous, the substrate universality is not good, and it is difficult to synthesize iodoallyl compounds with higher stereoselectivity, and it is impossible to achieve stereo divergent synthesis of iodoallyl compounds, such as patent technology document CN103254029A discloses a method for synthesizing 2-iodoallyl fluorine compounds, by simple allene, N-iodosuccinimide and triethylamine trihydrofluoride iodine fluoride reaction, synthesized E-type 2-iodoallyl fluorine compounds, but its reaction reagent is dangerous, substrate universality is not good, therefore, according to the above-mentioned related technology, it is urgent to develop a method for synthesizing iodoallyl compounds with stereo divergent. Summary of the invention

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

[0005] Based on the above purpose, the present invention provides a method for synthesizing iodine allyl compounds in a stereo divergent manner.

[0006] A method for synthesizing iodinated allyl compounds in a stereo-divergent manner, wherein the stereo-divergent method for synthesizing iodinated allyl compounds includes E-type iodinated allyl compounds and Z-type iodinated allyl compounds;

[0007] The E-type iodinated allyl compound is prepared from raw material A, raw material B, an organic solvent, a photocatalyst, and a base;

[0008] The Z-type iodoallyl compound is prepared from raw material A, raw material B, an organic solvent, a manganese catalyst, and a base;

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

[0010]

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

[0012]

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

[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 dimanganese decacarbonyl.

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

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

[0020] Step A2: The reaction solution is taken out from the glove box, reacted at room temperature under 420-430 nm irradiation for 35-45 h, and then spin-dried to obtain an E-type iodoallyl compound.

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

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

[0023] Step B1: adding a base to a reaction tube, then placing it in a glove box, sequentially adding a manganese catalyst, an organic solvent, raw material A and raw material B in the glove box, stirring for 25-30 minutes, and sealing the reaction tube to obtain a reaction solution;

[0024] Step B2: The reaction solution is taken out from the glove box, and the reaction solution is reacted for 2-5 hours under irradiation at room temperature at 450-460 nm, and then spin-dried to obtain a Z-type iodoallyl compound.

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

[0026] Beneficial effects of the present invention:

[0027] The present invention provides a novel method for synthesizing iodinated allyl compounds in a stereo-divergent manner, wherein the method has a wide substrate applicability and can prepare a variety of iodinated allyl compounds; at the same time, in the presence of a photocatalyst or a manganese catalyst and a base, high temperature and high pressure are not required, and the iodinated allyl compounds can be prepared in a stereo-divergent manner by irradiation with visible light, that is, the reaction conditions of the present invention are mild and the operation is simple; at the same time, the method has a wide substrate applicability and can prepare a variety of iodinated allyl compounds. By adopting a specific starting material, the starting material does not need to undergo any other treatment and modification, can be directly used for the reaction, has a small number of reaction steps, a simple process, and has a wide range of application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings in the following description are only for the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0029] Figure 1 1 is a reaction mechanism diagram of the E-type iodinated allyl compound and the Z-type iodinated allyl compound in the present invention. DETAILED DESCRIPTION

[0030] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

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

[0032] 2,4,5,6-Tetrakis(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) salt was purchased from Shanghai Haohong Biotechnology Co., Ltd.; (OC-6-22)-tris[2-(2,4-difluorophenyl)pyridine]iridium(III) was purchased from Zhengzhou Huiju Chemical Co., Ltd.; decacarbonyl dimanganese was purchased from Shanghai Jieshikai Biotechnology Co., Ltd.

[0033] Example 1: A method for synthesizing iodoallyl compounds in a stereo-divergent manner, comprising the following steps:

[0034] S1: 0.02 g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 0.5 g of potassium phosphate were added to a reaction tube, which was then placed in a glove box. 10 mL of toluene, 0.5 g of phenylacetylene and 2 g of iodoacetonitrile were added to the glove box, and the mixture was stirred for 25 min. The reaction tube was sealed to obtain a reaction solution.

[0035] S2: The reaction solution was taken out of the glove box, reacted under 420 nm irradiation at room temperature for 35 h, and then spin-dried to obtain an E-type iodoallyl compound with the following structural formula:

[0036]

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

[0038] S4: The reaction solution was taken out from the glove box, and the reaction solution was reacted for 2 h under 450 nm irradiation at room temperature and then spin-dried to obtain a Z-type iodoallyl compound with the following structural formula:

[0039]

[0040] Example 2: A method for synthesizing iodoallyl compounds in a stereo-divergent manner, comprising the following steps:

[0041] S1: 0.03 g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 0.6 g of cesium carbonate were added to a reaction tube in sequence, and then the tube was placed in a glove box. 12 mL of toluene, 0.6 g of 4-bromo-phenylacetylene and 2.1 g of iodoacetonitrile were added to the glove box, and the mixture was stirred for 26 min. The reaction tube was sealed to obtain a reaction solution.

[0042] S2: The reaction solution was taken out of the glove box, reacted for 36 hours under 422 nm irradiation at room temperature, and then spin-dried to obtain an E-type iodoallyl compound with the following structural formula:

[0043]

[0044] S3: 1.9 g of sodium carbonate was added to the reaction tube, which was then placed in a glove box, and 0.15 g of dimanganese decacarbonyl, 12 mL of toluene, 1.2 g of 4-bromo-phenylacetylene and 0.8 g of iodoacetonitrile were added in sequence in the glove box, stirred for 26 min, and the reaction tube was sealed to obtain a reaction solution;

[0045] S4: The reaction solution is taken out of the glove box, and the reaction solution is reacted for 2-5 hours under 452nm irradiation at room temperature, and then spin-dried to obtain a Z-type iodoallyl compound with the following structural formula:

[0046]

[0047] Example 3: A method for synthesizing iodoallyl compounds in a stereo-divergent manner, comprising the following steps:

[0048] S1: 0.04 g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 0.7 g of potassium phosphate were added to a reaction tube, which was then placed in a glove box. 14 mL of toluene, 0.7 g of 4-chloro-phenylacetylene and 2.3 g of iodoacetonitrile were added to the glove box, and the mixture was stirred for 27 min. The reaction tube was sealed to obtain a reaction solution.

[0049] S2: The reaction solution was taken out of the glove box, reacted under 424 nm irradiation at room temperature for 37 h, and then spin-dried to obtain an E-type iodoallyl compound with the following structural formula:

[0050]

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

[0052] S4: The reaction solution was taken out from the glove box, and the reaction solution was reacted for 3 hours under 455 nm irradiation at room temperature and then spin-dried to obtain a Z-type iodoallyl compound with the following structural formula:

[0053]

[0054] Example 4: A method for synthesizing iodoallyl compounds in a stereo-divergent manner, comprising the following steps:

[0055] S1: 0.03 g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 0.8 g of potassium phosphate were added to a reaction tube, which was then placed in a glove box. 18 mL of toluene, 0.8 g of 4-methoxy-phenylacetylene and 2.5 g of iodoacetonitrile were added to the glove box, and the mixture was stirred for 27 min. The reaction tube was sealed to obtain a reaction solution.

[0056] S2: The reaction solution was taken out of the glove box, reacted under 425 nm irradiation at room temperature for 38 h, and then spin-dried to obtain an E-type iodoallyl compound with the following structural formula:

[0057]

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

[0059] S4: The reaction solution was taken out from the glove box, and the reaction solution was reacted for 3 hours under 458 nm irradiation at room temperature and then spin-dried to obtain a Z-type iodoallyl compound with the following structural formula:

[0060]

[0061] Example 5: A method for synthesizing iodoallyl compounds in a stereo-divergent manner, comprising the following steps:

[0062] S1: 0.04 g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 0.8 g of cesium carbonate were added to a reaction tube in sequence, and then the tube was placed in a glove box. 20 mL of toluene, 1 g of 3-bromo-phenylacetylene and 2.5 g of iodoacetonitrile were added to the glove box, and the mixture was stirred for 28 min. The reaction tube was sealed to obtain a reaction solution.

[0063] S2: The reaction solution was taken out of the glove box, reacted under 428 nm irradiation at room temperature for 40 h, and then spin-dried to obtain an E-type iodoallyl compound with the following structural formula:

[0064]

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

[0066] S4: The reaction solution was taken out from the glove box, and the reaction solution was reacted for 4 hours under 458 nm irradiation at room temperature and then spin-dried to obtain a Z-type iodoallyl compound with the following structural formula:

[0067]

[0068] Example 6: A method for synthesizing iodoallyl compounds in a stereo-divergent manner, comprising the following steps:

[0069] S1: 0.04 g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 0.9 g of potassium phosphate were added to a reaction tube, which was then placed in a glove box. 28 mL of toluene, 1.1 g of 2-methoxy-phenylacetylene and 2.8 g of iodoacetonitrile were added to the glove box, and the mixture was stirred for 29 min. The reaction tube was sealed to obtain a reaction solution.

[0070] S2: The reaction solution was taken out of the glove box, reacted under 428 nm irradiation at room temperature for 42 hours, and then spin-dried to obtain an E-type iodoallyl compound with the following structural formula:

[0071]

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

[0073] S4: The reaction solution was taken out from the glove box, and the reaction solution was reacted for 4 hours under 458 nm irradiation at room temperature and then spin-dried to obtain a Z-type iodoallyl compound with the following structural formula:

[0074]

[0075] Example 7: A method for synthesizing iodoallyl compounds in a stereo-divergent manner, comprising the following steps:

[0076] S1: 0.05 g of bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium di(hexafluorophosphate) and 1 g of 1,2,2,6,6-pentamethylpiperidine were added to a reaction tube in sequence, and then the tube was placed in a glove box. 30 mL of dichloroethane, 1.2 g of phenylacetylene and 3 g of α-iododifluoroethane were added to the glove box, and the mixture was stirred for 30 min. The reaction tube was sealed to obtain a reaction solution.

[0077] S2: The reaction solution was taken out of the glove box, reacted under irradiation at 430 nm for 45 h at room temperature, and then spin-dried to obtain an E-type iodoallyl compound with the following structural formula:

[0078]

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

[0080] S4: The reaction solution was taken out from the glove box, and the reaction solution was reacted for 5 hours under 460 nm irradiation at room temperature and then spin-dried to obtain a Z-type iodoallyl compound with the following structural formula:

[0081]

[0082] Example 8: A method for synthesizing iodoallyl compounds in a stereo-divergent manner, comprising the following steps:

[0083] S1: 0.05 g of bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium di(hexafluorophosphate) and 1 g of 1,2,2,6,6-pentamethylpiperidine were added to a reaction tube in sequence, and then the tube was placed in a glove box. 30 mL of acetonitrile, 1.2 g of phenylacetylene and 3 g of N,N-dimethyl-α-iodoacetamide were added to the glove box, and the mixture was stirred for 30 min. The reaction tube was sealed to obtain a reaction solution.

[0084] S2: The reaction solution was taken out of the glove box, reacted under irradiation at 430 nm for 45 h at room temperature, and then spin-dried to obtain an E-type iodoallyl compound with the following structural formula:

[0085]

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

[0087] S4: The reaction solution was taken out from the glove box, and the reaction solution was reacted for 5 hours under 460 nm irradiation at room temperature and then spin-dried to obtain a Z-type iodoallyl compound with the following structural formula:

[0088]

[0089] Example 9: A method for synthesizing iodoallyl compounds in a stereo-divergent manner, comprising the following steps:

[0090] S1: 0.05 g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 1 g of 1,2,2,6,6-pentamethylpiperidine were added to a reaction tube in sequence, and then the tube was placed in a glove box. 30 mL of toluene, 1.2 g of 4-bromo-phenylacetylene and 3 g of tert-butyl α-iodoacetate were added to the glove box, and the mixture was stirred for 30 min. The reaction tube was sealed to obtain a reaction solution.

[0091] S2: The reaction solution was taken out of the glove box, reacted under irradiation at 430 nm for 45 h at room temperature, and then spin-dried to obtain an E-type iodoallyl compound with the following structural formula:

[0092]

[0093] S3: Add 2.2 g of cesium carbonate to a reaction tube, then put it into a glove box, add 0.3 g of decacarbonyl manganese, 30 mL of toluene, 3 g of 4-bromo-phenylacetylene and 2 g of tert-butyl α-iodoacetate in the glove box, stir for 30 min, seal the reaction tube, and obtain a reaction solution;

[0094] S4: The reaction solution was taken out from the glove box, and the reaction solution was reacted for 5 hours under 460 nm irradiation at room temperature and then spin-dried to obtain a Z-type iodoallyl compound with the following structural formula:

[0095]

[0096] Example 10: A method for synthesizing iodoallyl compounds in a stereo-divergent manner, comprising the following steps:

[0097] S1: 0.05 g of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile and 1 g of 1,2,2,6,6-pentamethylpiperidine were added to a reaction tube in sequence, and then the tube was placed in a glove box. 30 mL of toluene, 1.2 g of 4-methoxy-phenylacetylene and 3 g of tert-butyl α-iodoacetate were added to the glove box, and the mixture was stirred for 30 min. The reaction tube was sealed to obtain a reaction solution.

[0098] S2: The reaction solution was taken out of the glove box, reacted under irradiation at 430 nm for 45 h at room temperature, and then spin-dried to obtain an E-type iodoallyl compound with the following structural formula:

[0099]

[0100] S3: Add 2.2 g of cesium carbonate to a reaction tube, then put it into a glove box, add 0.3 g of decacarbonyl manganese, 30 mL of toluene, 3 g of 4-methoxy-phenylacetylene and 2 g of tert-butyl α-iodoacetate in the glove box, stir for 30 min, seal the reaction tube, and obtain a reaction solution;

[0101] S4: The reaction solution was taken out from the glove box, and the reaction solution was reacted for 5 hours under 460 nm irradiation at room temperature and then spin-dried to obtain a Z-type iodoallyl compound with the following structural formula:

[0102]

[0103] Example 11: A method for synthesizing iodoallyl compounds in a stereo-divergent manner, comprising the following steps:

[0104] S1: 0.05 g of bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium di(hexafluorophosphate) and 1 g of 1,2,2,6,6-pentamethylpiperidine were added to a reaction tube in sequence, and then the tube was placed in a glove box. 30 mL of toluene, 1.2 g of 4-ethynylbenzonitrile and 3 g of α-iodotrifluoroethane were added to the glove box, and the mixture was stirred for 30 min. The reaction tube was sealed to obtain a reaction solution.

[0105] S2: The reaction solution was taken out of the glove box, reacted under irradiation at 430 nm for 45 h at room temperature, and then spin-dried to obtain an E-type iodoallyl compound with the following structural formula:

[0106]

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

[0108] S4: The reaction solution was taken out from the glove box, and the reaction solution was reacted for 5 hours under 460 nm irradiation at room temperature and then spin-dried to obtain a Z-type iodoallyl compound with the following structural formula:

[0109]

[0110] Performance Testing:

[0111] Dibromomethane was added as an internal standard to the E-type iodinated allyl compound and the Z-type iodinated allyl compound prepared in Example 1 to Example 11, and nuclear magnetic resonance and high-resolution characterization were performed, and the nuclear magnetic resonance yield and the ratio between the E-type iodinated allyl compound and the Z-type iodinated allyl compound in the preparation process were tested; then the product was purified by silica gel column chromatography, and its properties were observed, and its yield and the ratio between the E-type iodinated allyl compound and the Z-type iodinated allyl compound in the preparation process were calculated.

[0112] Table 1 Summary of experimental data in Examples 1 to 11

[0113]

[0114]

[0115] Data Analysis:

[0116] As can be seen from Table 1, the stereo divergent synthesis of iodinated allyl compounds prepared by the present invention has a higher yield and higher stereoselectivity; the present invention provides a novel method for synthesizing iodinated allyl compounds in a stereo divergent manner, the method substrate has a wide applicability, and a variety of iodinated allyl compounds can be prepared; at the same time, in the presence of a photocatalyst or a manganese catalyst and a base, high temperature and high pressure are not required, and the iodinated allyl compounds can be prepared stereo divergently by visible light irradiation, that is, the reaction conditions of the present invention are mild and the operation is simple; at the same time, the substrate applicability of the method is wide, and a variety of iodinated allyl compounds can be prepared. By adopting a specific starting material, the starting material does not need to undergo any other treatment and modification, can be directly used for 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 were 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 subjected to 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 were 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 subjected to 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 were 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 subjected to 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 were 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 subjected to 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 subjected to 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 subjected to 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 were 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 subjected to 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 subjected to 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 subjected to 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 subjected to 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;Found338.0015.

[0174] The Z-type iodoallyl compound prepared in Example 8 was subjected to 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;Found338.0016.

[0178] The E-type iodoallyl compound prepared in Example 9 was subjected to 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 subjected to 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 subjected to 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 subjected to 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 subjected to 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 subjected to 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 illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

[0205] The present 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 the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for synthesizing iodoallyl compounds in a stereo-divergent manner, characterized in that: The stereo divergent synthesis of iodinated allyl compounds includes E-type iodinated allyl compounds and Z-type iodinated allyl compounds; The E-type iodinated allyl compound is prepared from raw material A, raw material B, an organic solvent, a photocatalyst, and a base; The Z-type iodoallyl compound is prepared from raw material A, raw material B, an organic solvent, a manganese catalyst, and a base; The structural formula of the raw material A is as follows: The structural formula of the raw material B is as follows: The R 1 is an aryl group; R 2 is hydrogen; R 3 It is any one of a cyano group, a trifluoromethyl group, a difluoromethyl group, an ester group and an amide group.

2. The method for synthesizing iodoallyl compounds in a stereo divergent manner according to claim 1, characterized in that: The organic solvent is any one of dichloroethane, toluene and acetonitrile.

3. The method for synthesizing iodoallyl compounds in a stereo divergent manner according to claim 1, characterized in that: 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).

4. The method for synthesizing iodoallyl compounds in a stereo divergent manner 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.

5. The method for synthesizing iodoallyl compounds in a stereo divergent manner according to claim 1, characterized in that: The manganese catalyst is dimanganese decacarbonyl.

6. The method for synthesizing iodoallyl compounds in a stereo divergent manner according to claim 1, characterized in that: The preparation method of the E-type iodoallyl compound is as follows: Step A1: Add a photocatalyst and a base to a reaction tube in sequence, then put it into a glove box, add an organic solvent, raw material A and raw material B in the glove box, stir for 25-30 minutes, seal the reaction tube, and obtain a reaction solution; Step A2: The reaction solution is taken out from the glove box, reacted at room temperature under 420-430 nm irradiation for 35-45 h, and then spin-dried to obtain an E-type iodoallyl compound.

7. The method for synthesizing iodoallyl compounds in a stereo divergent manner according to claim 6, characterized in that: The usage ratio of the photocatalyst, base, 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.

8. The method for synthesizing iodoallyl compounds in a stereo divergent manner according to claim 1, characterized in that: The preparation method of the Z-type iodoallyl compound is as follows: Step B1: adding a base to a reaction tube, then placing it in a glove box, sequentially adding a manganese catalyst, an organic solvent, raw material A and raw material B in the glove box, stirring for 25-30 minutes, and sealing the reaction tube to obtain a reaction solution; Step B2: The reaction solution is taken out from the glove box, and the reaction solution is reacted for 2-5 hours under irradiation at room temperature at 450-460 nm, and then spin-dried to obtain a Z-type iodoallyl compound.

9. The method for synthesizing iodoallyl compounds in a stereo divergent manner according to claim 8, characterized in that: The usage ratio of the base, the manganese catalyst, the organic solvent, the raw material A and the raw material B in step B1 is 1.8-2.2 g: 0.1-0.3 g: 10-30 mL: 1-3 g: 0.5-2 g.

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