A method for blue light-induced trifluoromethylation of alkynyl compounds

Abstract

The present invention develops a method for blue light induced hydrogen trifluoromethylation of alkynyl compounds. The method uses alkynyl compounds and sodium trifluoromethanesulfinate as raw materials, and uses sodium trifluoromethanesulfinate as a trifluoromethyl source to carry out hydrogen trifluoromethylation of alkynyl groups under blue light irradiation at room temperature to obtain C-containing vinyl This method has the advantages of a wide substrate range, mild reaction conditions, high yield of target product, simple reaction operation, low reaction pollution, and is feasible for industrial large-scale production.

Description

Technical Field

[0001] The present invention relates to a method for blue light induced trifluoromethylation of alkynyl compounds, and in particular to a method for synthesizing C-containing alkynyl compounds by using blue light induced alkynyl compounds and sodium trifluoromethanesulfinate. vinyl The invention discloses a method for forming an alkenyl compound with a -CF3 bond, and belongs to the field of organic chemistry. Background Art

[0002] Fluorine atoms can change the stability and permeability of organic drugs, enhance the lipid solubility of compounds, and also reduce the development of drug resistance. Therefore, the introduction of fluorine atoms into drug molecules is a common method in drug synthesis and drug design. However, due to the high activity of fluorine atoms themselves, it is difficult to control them in the reaction. Therefore, the introduction of fluorine atoms is mostly achieved by introducing fluorine-containing groups, among which trifluoromethyl is one of the commonly used methods for introducing fluorine atoms. vinyl Alkenyl compounds with -CF3 bonds are important components of drug molecules and play a very important role in drugs such as panomifen, cyhalothrin, anti-inflammatory drugs, and anti-tumor drugs.

[0003] Many constructs of C vinyl -CF3 bond methods, many of which use olefin derivatives to construct C vinyl -CF3 alkenyl compounds, such as α, β-unsaturated boronic acid, α, β-unsaturated nitro compounds, α, β-unsaturated carboxylic acids, etc., the raw materials required by this method need to be synthesized in one or more steps, and the steps are relatively cumbersome. vinyl The -CF3 bond is relatively simple. The hydrogen trifluoromethylation of alkynyl compounds can be achieved by different trifluoromethylation reagents. Commonly used trifluoromethylation reagents include Umemoto's reagent, Togni's reagent, CF3X (X = I, Br, H), CF3SO2Na, etc. Among them, Umemoto's reagent and Togni's reagent are relatively expensive, and CF3X (X = I, Br, H) is a gas, which is not conducive to operation, while CF3SO2Na is cheap and stable, which has great advantages. It has been reported that it is used for the hydrogen trifluoromethylation of alkynyl compounds. However, the method used requires the participation of peroxides and requires high temperature, and the conditions are relatively harsh. Therefore, a simple and mild method is developed to synthesize C-containing compounds using sodium trifluoromethanesulfinate as a trifluoromethylation reagent. vinyl The alkenyl compounds of -CF3 are important. Summary of the Invention

[0004] In order to solve the defects of existing synthesis methods, we have developed a method for the blue light induced trifluoromethylation of alkynyl compounds. This method uses alkynyl compounds and sodium trifluoromethanesulfinate as raw materials, and uses sodium trifluoromethanesulfinate as the trifluoromethyl source under blue light irradiation to carry out the trifluoromethylation reaction of alkynyl groups at room temperature. vinyl -CF3 bond alkenyl compounds.

[0005] In order to achieve the above-mentioned object of the invention, the present invention proposes the following technical solutions:

[0006]

[0007] This scheme is to react alkynyl compound I with sodium trifluoromethylsulfinate II in the presence of photocatalyst 3DPA2FBN and water, using a mixed solution of dimethyl sulfoxide and N,N-dimethylformamide as solvent, and sodium trifluoromethylsulfinate as a trifluoromethyl source under blue light irradiation at room temperature to carry out a hydrogen trifluoromethylation reaction of the alkynyl group to obtain a C-containing compound. vinyl -CF3 bond alkenyl compound III.

[0008] As a preferred embodiment, the alkynyl compound I has a structure shown in Formula 1:

[0009]

[0010] Wherein, R is H, various substituted hydrocarbon groups, various substituted silicon groups; R' is H, various substituted hydrocarbon groups, various substituted silicon groups; the hydrocarbon groups are straight-chain alkyl groups, alkyl groups with branches or aromatic groups, and aromatic groups. In the alkynyl compounds of the present invention, R and R' can be H, various substituted straight-chain alkyl groups such as C 10 Straight-chain alkyl groups, alkyl groups with branches or aromatic groups such as 1-methyl-1-hydroxybenzyl, aromatic groups such as 4-methoxyphenyl, including mono-substituted and poly-substituted hydrocarbon groups, and the position of the substituents is not limited; silicon groups such as trimethylsilyl.

[0011] As a preferred solution, the sodium trifluoromethanesulfinate II has a structure shown in Formula 2:

[0012] CF3SO2Na

[0013] Formula 2

[0014] As a preferred solution, the vinyl -CF3 bond alkenyl compound III has the structure shown in formula 3:

[0015]

[0016] Wherein, R is H, various substituted hydrocarbon groups, various substituted silicon groups; R' is H, various substituted hydrocarbon groups, various substituted silicon groups; the hydrocarbon groups are straight-chain alkyl groups, alkyl groups with branches or aromatic groups, and aromatic groups.

[0017] As a preferred embodiment, the molar amount of sodium trifluoromethanesulfinate is 1.5 to 3 times the molar amount of the alkynyl compound. Increasing the proportion of sodium trifluoromethanesulfinate significantly improves the yield of the target product. When the proportion of sodium trifluoromethanesulfinate exceeds 3 times that of the alkynyl compound, the yield of the target product does not significantly increase.

[0018] As a preferred solution, the molar amount of the 3DPA2FBN is 0.5-1% of the molar amount of the alkynyl compound. When the amount of the photocatalyst reaches 1%, the yield of the target product of the reaction is good.

[0019] As a preferred embodiment, the reaction solvent is a mixed solvent of dimethyl sulfoxide and N,N-dimethylformamide, wherein the ratio of dimethyl sulfoxide to N,N-dimethylformamide is 2:1 to 4:1. Changing the ratio of dimethyl sulfoxide to N,N-dimethylformamide in the mixed solvent significantly affects the yield of the target product.

[0020] The specific reaction mechanism of the hydrotrifluoromethylation reaction between the alkynyl compound of the present invention and sodium trifluoromethanesulfinate is as follows: the photocatalyst 3DPA2FBN (PC) changes from the ground state to the excited state under blue light, and then undergoes single electron transfer (SET) with sodium trifluoromethanesulfinate to generate a free radical anion PC. ·- , CF3 and SO2, and then the trifluoromethyl radical produced reacts with the alkynyl to produce an alkenyl radical, which then reacts with the radical anion PC ·- Single electron transfer (SET) occurs to obtain an olefin anion, and the photocatalyst (PC) returns to the ground state. Finally, the olefin anion obtains a hydrogen proton from water to finally obtain the target compound.

[0021] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0022] First, the method does not require transition metals, peroxides, and heating;

[0023] Second, the method is highly efficient, requiring only 1% of the photocatalyst to achieve a yield of up to 94%, and is tolerant to a variety of functional groups.

[0024] Third, this method is simple, mild, green and can effectively synthesize C vinyl -CF3 alkenyl compounds;

[0025] Fourth, alkynyl drug molecules can be smoothly converted to C-containingvinyl -CF3 alkenyl compounds;

[0026] Fifth, this method has certain feasibility for industrial large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The proposed method is for the blue light-induced trifluoromethylation of alkynyl compounds; Figure 2 is the hydrogen nuclear magnetic resonance spectrum of (E)-5,5,5-trifluoro-2-(pyridin-4-yl)pent-3-en-2-ol; Figure 3 is the carbon NMR spectrum of (E)-5,5,5-trifluoro-2-(pyridin-4-yl)pent-3-en-2-ol; Figure 4 This is the NMR fluorine spectrum of (E)-5,5,5-trifluoro-2-(pyridin-4-yl)pent-3-en-2-ol. DETAILED DESCRIPTION

[0028] To make the above-mentioned features, advantages, and purposes of the present invention more clearly understood, the present invention is described in detail below in conjunction with specific embodiments. The above description sets forth many specific details to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art can make similar modifications without violating the scope of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0029] Unless otherwise specified, the reaction raw materials and catalysts involved in the following examples are conventional commercially available reagents on the market.

[0030] Condition optimization experiment: Taking the synthesis of (E)-5,5,5-trifluoro-2-phenylpentyl-3-ene-2-ol from 2-phenyl-3-butyn-2-ol and sodium trifluoromethanesulfinate as an example, the optimal reaction conditions were obtained by optimizing the reactant ratio, light source, photocatalyst type, solvent selection, mixed solvent ratio, etc., and monitoring the reaction yield by gas chromatography. The specific reaction under the optimal reaction conditions is as follows:

[0031] To a 10 mL reaction tube, 0.1 mmol of 2-phenyl-3-butyn-2-ol, 0.3 mmol of sodium trifluoromethanesulfinate, 1% mmol of 3DPA2FBN, and 0.3 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed for 12 hours at room temperature under irradiation with a 24 W blue light source at a wavelength of 450-465 nm. After completion of the reaction, column chromatography using a solvent mixture of petroleum ether and ethyl acetate yielded the target product, (E)-5,5,5-trifluoro-2-phenylpentyl-3-ene-2-ol, as a yellow liquid in an 83% yield.

[0032]

[0033]

[0034] From the experimental groups 2 to 3 in the above table, it can be seen that when there is no light or no photocatalyst, the reaction does not occur. It can be seen that light and photocatalyst are indispensable for the reaction to proceed.

[0035] From the experimental groups 1 and 4 to 6 in the above table, it can be seen that as the amount of sodium trifluoromethanesulfinate increases, the yield of the target product also increases. When 0.3 mmol of sodium trifluoromethanesulfinate is added, the yield of the target product of the reaction is the best. When 0.4 mmol of sodium trifluoromethanesulfinate is added, the yield of the target product of the reaction decreases slightly.

[0036] From experimental groups 1 and 7 to 14 in the above table, it can be seen that when the wavelength of light is 450-465nm, the yield of the target product of the reaction is the best. Increasing or decreasing the wavelength will make the reaction effect worse. Among them, white light also has a good reaction effect.

[0037] From the experimental groups 1 and 15 to 17 in the above table, we can see that different photocatalysts have different effects on the reaction, among which Mes-Acr + ClO4 - Cu(dmp)(DPEPhos)BF4 had little effect on the reaction, 4CzIPN could obtain the target product with a yield of 73%, and 3DPA2FBN had the best reaction effect.

[0038] As can be seen from Experimental Groups 1 and 18-29 in the table above, highly polar solvents such as methanol, ethanol, and acetonitrile showed only trace amounts of reaction, while dimethyl sulfoxide, N,N-dimethylformamide, and acetone all showed good results. However, the reaction was essentially nonexistent in solvents of medium and weak polarity. The best reaction was achieved when using a dimethyl sulfoxide / N,N-dimethylformamide ratio of 2:1 as the solvent.

[0039] The present invention will be further described below with reference to specific Preparation Examples 1 to 33:

[0040] Preparation Example 1

[0041] To a 10 mL reaction tube, 0.3 mmol of N-propynylphthalamide, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. Column chromatography was performed to obtain 2-(4,4,4-trifluorobut-2-en-1-yl)isoindole-1,3-dione as a white solid in 82% yield (E / Z = 1.5:1).

[0042] 1 H NMR (400MHz, CDCl3) δ7.85(q,J=4.8Hz,2H),7.73(q,J=4.8Hz,2H),6.40(ddq,J=15.7,5.5,2.3Hz,0.6H),5.9 7(dq,J=12.1,6.2Hz,0.4H),5.88–5.61(m,1H),4.58(dt,J=6.4,2.1Hz,0.8H),4.38(dt,J=5.3,2.1Hz,1.2H).

[0043] 13 C NMR(101MHz, CDCl3)δ167.53,167.43,136.28(q,J=5.1Hz),134.28,134.19,133.54(q,J=6.5Hz),131.79,131.73,123.52, 123.42, 122.65 (q, J = 271.9Hz), 122.41 (q, J = 269.6Hz), 120.94 (q, J = 34.4Hz), 120.22 (q, J = 34.8Hz), 37.51, 35.26, 35.24.

[0044] 19 F NMR (376MHz, CDCl3) δ-59.08,-64.44.

[0045] Preparation Example 2

[0046] To a 10 mL reaction tube, 0.3 mmol of 4-ethylphenylacetylene, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. 1-Ethyl-4-(3,3,3-trifluoropropyl-1-en-1-yl)benzene was isolated by column chromatography as a yellow liquid with a yield of 77% (E / Z = 1:1.6).

[0047] 1 H NMR (400MHz, CDCl3) δ7.37(dd,J=11.6,8.0Hz,2H),7.22(dd,J=8.1,6.1Hz,2H),7.17–7.07(m,0.39H),6.89(d,J=12.7Hz ,0.61H),6.16(dq,J=16.1,6.6Hz,0.39H),5.71(dq,J=12.6,9.2Hz,0.61H),2.68(q,J=7.6Hz,2H),1.25(t,J=7.5Hz,3H).

[0048] 13 C NMR (101MHz, CDCl3) δ146.60, 145.55, 139.64 (q, J = 5.9Hz), 137.55 (q, J = 6.9Hz), 130.95, 130.90, 129.16 (q, J = 2.6Hz), 128.43, 127. 86,127.56,123.78(q,J=268.3Hz),122.94(q,J=271.1Hz),117.00(q,J=35.0Hz),114.83(q,J=33.8Hz),28.71,28.64,15.33,15.26.

[0049] 19 F NMR (376MHz, CDCl3) δ-57.55,-63.12.

[0050] Preparation Example 3

[0051] To a 10 mL reaction tube, 0.3 mmol of 4-methoxyphenylacetylene, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. Column chromatography separated the product to yield 1-methoxy-4-(3,3,3-trifluoropropyl-1-en-1-yl)benzene as a yellow liquid in a 71% yield (E / Z = 1:1.9).

[0052] 1 H NMR (400MHz, CDCl3) δ7.39 (dd, J=8.8, 2.2Hz, 2H), 7.09 (dq, J=16.1, 2.3Hz, 0.35H), 6.94–6.87 (m, 2H), 6.82 (d, J=12.6Hz,0.65H),6.07(dq,J=16.1,6.6Hz,0.35H),5.64(dq,J=12.6,9.3Hz,0.65H),3.84(s,1H),3.83(s,2H).

[0053] 13 C NMR (101MHz, CDCl3) δ161.04, 160.32, 139.17 (q, J = 6.1Hz), 137.09 (q, J = 6.9Hz), 133.58, 130.89 (q, J = 2.8Hz), 129.01, 126.07, 126. 05,123.91(q,J=268.4Hz),123.08(d,J=270.8Hz),115.66(q,J=35.0Hz),114.31,113.78,113.42(q,J=67.6,33.9Hz),55.34,55.26.

[0054] 19 F NMR (376MHz, CDCl3) δ-57.55,-62.85.

[0055] Preparation Example 4

[0056] To a 10 mL reaction tube, 0.3 mmol of methyl 4-ethynylbenzoate, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. Methyl 4-(3,3,3-trifluoroprop-1-en-1-yl)benzoate was isolated by column chromatography as a white solid in 84% yield (E / Z = 1.1:1).

[0057] 1 H NMR (400MHz, CDCl3) δ8.05(t,J=8.6Hz,2H),7.52(d,J=8.2Hz,1H),7.44(d,J=8.1Hz,1H),7.18(dq,J=16.1,2.3Hz,0.53H),6. 97(d,J=12.6Hz,0.49H),6.30(dq,J=16.1,6.4Hz,0.53H),5.87(dq,J=12.6,8.8Hz,0.49H),3.93(s,1.59H),3.93(s,1.41H).

[0058] 13 C NMR (101MHz, CDCl3) δ166.52,166.36,138.54(q,J=5.8Hz),138.10,137.57,136.60(q,J=6.7Hz),131.31,130.38,130.15,129.51,12 8.75(q,J=2.5Hz),127.45,123.22(q,J=269.2Hz),122.46(q,J=271.6Hz),119.88(q,J=35.0Hz),118.16(q,J=34.3Hz),52.30,52.23.

[0059] 19 F NMR (376MHz, CDCl3) δ-57.65,-63.68.

[0060] Preparation Example 5

[0061] To a 10 mL reaction tube, 0.3 mmol of 4-ethylbiphenylacetylene, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. Column chromatography separation yielded 4-ethyl-4'-(3,3,3-trifluoroprop-1-en-1-yl)-1,1'-biphenyl as a white solid in 53% yield (E / Z = 1.2:1).

[0062] 1 H NMR (400MHz, CDCl3) δ7.62 (dd, J=8.4, 6.5Hz, 2H), 7.57–7.46 (m, 4H), 7.30 (dd, J=8.3, 2.5Hz, 2H), 7.1 9(dq,J=16.1,2.2Hz,0.54H), 6.94(d,J=12.6Hz,0.46H), 2.72(q,J=7.6Hz,2H), 1.29(t,J=7.6Hz,3H).

[0063] 13 C NMR (101MHz, CDCl3) δ144.12, 143.95, 142.76, 141.85, 139.29 (q, J = 6.0Hz), 137. 57,137.42,137.24(q,J=6.8Hz),132.14,132.02,129.58(q,J=2.6Hz),128.44,1 28.38,127.96,127.35,126.98,126.94,126.80,123.69(q,J=268.4Hz),122.88( q, J=271.2Hz), 117.57 (q, J=35.2Hz), 115.46 (q, J=33.7Hz), 28.53, 15.55, 15.53.

[0064] 19 F NMR(376MHz, CDCl3)δ-57.49,-63.14.

[0065] Preparation Example 6

[0066] To a 10 mL reaction tube, 0.3 mmol of 1-dodecyne, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. Column chromatography separated the product into 1,1,1-trifluorotrideca-2-ene, a colorless liquid with a yield of 57% (E / Z = 1:1.9).

[0067] 1 H NMR(400MHz, CDCl3)δ6.38(dtq,J=15.9,6.8,2.2Hz,0.33H),5.98(dq,J=11.6,7.9Hz,0.66H),5.80–5.32(m,1 H),2.50–2.21(m,1.32H),2.21–2.08(m,0.68H),1.56–1.35(m,2H),1.36–1.12(m,14H),0.88(t,J=6.8Hz,3H).

[0068] 13 C NMR (101MHz, CDCl3) δ 143.22 (q, J = 5.4Hz), 140.83 (q, J = 6.4Hz), 123.40 (q, J = 271.6Hz), 123.14 (q, J = 269.0Hz), 118.26 (q, J = 33.2Hz), 118. 21(q,J=33.2Hz),31.90,31.45,29.58,29.53,29.51,29.36,29.34,2 9.32,29.10,29.03,28.87,28.86,28.35,27.96,27.95,22.68,14.08.

[0069] 19 F NMR (376MHz, CDCl3) δ-58.08,-63.93.

[0070] Preparation Example 7

[0071] To a 10 mL reaction tube, 0.3 mmol of 2-(pentyl-4-yn-1-yl)-1,3-diphenylpropane-1,3-dione, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. Column chromatography was performed to obtain 1,3-diphenyl-2-(6,6,6-trifluoro-4-en-1-yl)propane-1,3-dione as a colorless liquid with a yield of 68% (E / Z = 1:1.3).

[0072] 1 H NMR (400MHz, CDCl3) δ7.96 (dt, J=8.6, 1.4Hz, 4H), 7.56 (td, J=7.2, 1.4Hz, 2H), 7.45 ( td,J=7.7,7.2,1.3Hz,4H),6.34(dtq,J=15.7,6.7,2.2Hz,0.44H),5.97(dt,J=11.6,7 .7Hz,0.53H),5.69–5.50(m,1H),5.22(td,J=6.6,1.9Hz,1H),2.36(ddq,J=9.7,4.5, 2.3Hz,1H),2.21(ddq,J=10.1,4.9,2.4Hz,1H),2.18–2.09(m,2H),1.66–1.50(m,2H).

[0073] 13 C NMR (101MHz, CDCl3) δ195.86,195.84,141.98(q,J=5.4Hz),139.67(q,J=6.6Hz),135.87,135.83,133.60,133.56,128.89,128.88,128.45,1 23.20(q,J=271.8Hz),122.91(q,J=269.1Hz),118.86(q,J=33.3Hz),118.82(q,J=33.3Hz),56.77,56.64,31.28,28.74,28.10,27.22,26.41.

[0074] 19 F NMR (376MHz, CDCl3) δ-58.03,-63.91.

[0075] Preparation Example 8

[0076] To a 10 mL reaction tube, 0.3 mmol of 1-(tert-butyl)-4-(hexyl-5-yn-1-yloxy)benzene, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. 1-(tert-butyl)-4-((7,7,7-trifluorohept-5-en-1-yl)oxy)benzene was isolated by column chromatography as a colorless liquid with a yield of 78% (E / Z = 1:1.1).

[0077] 1 H NMR (400MHz, CDCl3) δ7.34(d,J=8.7Hz,2H),6.87(d,J=8.7Hz,2H),6.50–6.37(m,0.48H),6.03(dq,J=11.7,7.8Hz,0.52H),5.76–5.54(m,1H),3 .99(t,J=6.0Hz,2H),2.42(qt,J=7.7,2.3Hz,1H),2.26(qt,J=8.0,5.9, 2.9Hz,1H),1.94–1.76(m,2H),1.67(qd,J=8.0,5.4Hz,2H),1.34(s,9H).

[0078] 13 C NMR (101MHz, CDCl3) δ156.71,156.65,143.33,143.27,142.60(q,J=5.4Hz),140.25(q,J=6.6Hz),126.21,126.19,123.32(q,J=271.8Hz ), 123.04 (q, J = 269.1Hz), 118.70 (q, J = 33.4Hz), 113.88, 113.86, 67.31, 67.29, 34.02, 31.49, 31.10, 28.75, 28.68, 28.02, 25.44, 24.60.

[0079] 19 F NMR(376MHz, CDCl3)δ-58.00,-63.91.

[0080] Preparation Example 9

[0081] To a 10 mL reaction tube, 0.3 mmol of but-3-yn-1-yl benzoate, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. 5,5,5-trifluoropent-3-en-1-yl benzoate was isolated by column chromatography as a colorless liquid with a yield of 72% (E / Z = 3:1).

[0082] 1 H NMR(400MHz, CDCl3)δ8.04(d,J=7.8Hz,2H),7.68–7.51(m,1H),7.45(td,J=7.8,1.6Hz,2H),6.46(dtq,J=16.2,6.9,2.6,2.2Hz,0.25H), 6.11(dq,J=11.6,7.6Hz,0.75H),5.89–5.62(m,1H),4.42(t,J=6.3Hz,2H),2.80(qq,J=6.3,2.0Hz,1.5H),2.64(dq,J=6.5,2.1Hz,0.5H).

[0083] 13 C NMR(101MHz, CDCl3)δ166.40,166.32,138.08(q,J=5.4Hz),136.11(q,J=6.5Hz),133.13,133.08,129.89,129.86,129.56, 129.54, 128.42, 128.38, 123.03 (q, J = 272.0Hz), 120.95 (q, J = 33.6Hz), 120.85 (q, J = 33.7Hz), 63.04, 62.52, 30.92, 27.95.

[0084] 19 F NMR (376MHz, CDCl3) δ-58.33,-64.38.

[0085] Preparation Example 10

[0086] To a 10 mL reaction tube, 0.3 mmol of 1-ethyl-4-[2-(4-methoxyphenyl)ethynyl]benzene, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. Column chromatography separated the resulting mixture of (Z)-1-ethyl-4-(3,3,3-trifluoro-1-(4-methoxyphenyl)prop-1-en-2-yl)benzene and (Z)-1-ethyl-4-(3,3,3-trifluoro-2-(4-methoxyphenyl)prop-1-en-1-yl)benzene as a yellow liquid in a 52% yield.

[0087] 1 H NMR (400MHz, CDCl3) δ7.21 (dd, J=7.9, 4.3Hz, 3H), 7.16 (q, J=1.9Hz, 0.45H), 7.13 (q, J=1.9Hz, 0.55H), 7.01 (d, J=8.3Hz, 1H), 6.99–6.90 (m, 3H), 6.73 –6.64(m,1H),3.85(s,1.35H),3.75(s,1.65H),2.70(q,J=7.6Hz,1.1H),2. 58(q,J=7.6Hz,0.9H),1.28(t,J=7.6Hz,1.64H),1.18(t,J=7.6Hz,1.36H).

[0088] 13 C NMR (101MHz, CDCl3) δ159.92,159.81,145.24,144.74,132.85(q,J=5.7Hz),132.31(q,J=6.1Hz),131.60,131.11,131.07,130.18,130.09,129. 80,128.48,127.79,126.22,124.99,124.06(q,J=272.9Hz),123.97(q, J=273.3Hz),114.40,113.66,55.21,55.17,28.62,28.55,15.28,15.14.

[0089] 19 F NMR (376MHz, CDCl3) δ-65.61,-65.92.

[0090] Preparation Example 11

[0091] To a 10 mL reaction tube, 0.3 mmol of (4-methoxyphenylethynyl)trimethylsilane, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-Trimethyl(3,3,3-trifluoro-1-(4-methoxyphenyl)prop-1-en-2-yl)silane was isolated by column chromatography as a yellow liquid in a 41% yield.

[0092] 1 H NMR (400MHz, CDCl3) δ7.81 (q, J = 2.6Hz, 1H), 7.18 (d, J = 8.6Hz, 2H), 6.88 (d, J = 8.7Hz, 2H), 3.83 (s, 3H), 0.08 (s, 9H).

[0093] 13 C NMR (101MHz, CDCl3) δ159.85, 147.84 (q, J = 9.4Hz), 132.31 (q, J = 27.8Hz), 129.75, 129.23, 126.62 (q, J = 274.6Hz), 113.49, 55.25, 0.30.

[0094] 19 F NMR (376MHz,CDCl3)δ-58.66.

[0095] Preparation Example 12

[0096] To a 10 mL reaction tube, 0.3 mmol of 2-phenyl-3-butyn-2-ol, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-5,5,5-trifluoro-2-phenylpent-3-en-2-ol was isolated by column chromatography as a yellow liquid in an 83% yield.

[0097] 1 H NMR (400MHz, CDCl3) δ7.47–7.42(m,2H),7.42–7.35(m,2H),7.34–7.29(m,1H),6.6 3(dq,J=15.6,2.1Hz,1H),5.99(dq,J=15.6,6.5Hz,1H),2.18(s,1H),1.72(s,3H).

[0098] 13 C NMR (101MHz, CDCl3) δ 145.65 (q, J = 6.1Hz), 144.36, 128.65, 127.80, 125.05, 123.43 (q, J = 269.3Hz), 116.19 (q, J = 33.9Hz), 73.61, 28.92.

[0099] 19 F NMR (376 MHz, CDCl3) δ-63.70.

[0100] Preparation Example 13

[0101] To a 10 mL reaction tube, 0.3 mmol of 1,1-diphenyl-2-propyn-1-ol, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-4,4,4-trifluoro-1,1-diphenylbut-2-en-1-ol was isolated by column chromatography as a colorless liquid in an 82% yield.

[0102] 1 H NMR (400MHz, CDCl3) δ7.43–7.28(m,10H),6.98(dq,J=15.6,1.8Hz,1H),6.11(dq,J=15.8,6.5Hz,1H),2.35(s,1H).

[0103] 13 C NMR (101MHz, CDCl3) δ 144.37 (q, J = 6.0Hz), 144.11, 128.57, 128.02, 126.72, 123.45 (q, J = 269.5Hz), 117.38 (q, J = 34.0Hz), 78.31.

[0104] 19 F NMR (376MHz, CDCl3) δ-63.44

[0105] Preparation Example 14

[0106] To a 10 mL reaction tube, 0.3 mmol of 1-ethynylcyclohexanol, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-1-(3,3,3-trifluoroprop-1-en-1-yl)cyclohexane-1-ol was isolated by column chromatography as a yellow liquid in an 89% yield.

[0107] 1 H NMR (400MHz, CDCl3) δ6.45 (dq, J=15.7, 2.2Hz, 1H), 5.90 (dq, J=15.7, 6.5Hz, 1H), 1.78–1.44 (m, 10H).

[0108] 13 C NMR (101MHz, CDCl3) δ146.85 (q, J = 6.0Hz), 123.60 (q, J = 269.3Hz), 116.01 (q, J = 33.7Hz), 71.14, 37.04, 25.11, 21.45.

[0109] 19 F NMR (376MHz,CDCl3)δ-63.71.

[0110] Preparation Example 15

[0111] To a 10 mL reaction tube, 0.3 mmol of 3,5-dimethyl-1-hexyn-3-ol, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-1,1,1-trifluoro-4,6-dimethylhept-2-en-4-ol was isolated by column chromatography as a colorless liquid in a 61% yield.

[0112] 1 H NMR (400MHz, CDCl3) δ6.40 (dq, J=15.7, 2.1Hz, 1H), 5.89 (dq, J=15.6, 6.5Hz, 1H), 1.74 (dp, J=13.1,6.5Hz,1H),1.51(dd,J=6.1,1.3Hz,2H),1.33(s,3H),0.94(dd,J=11.0,6.6Hz,6H).

[0113] 13 C NMR (101MHz, CDCl3) δ 146.64 (q, J = 5.9Hz), 123.53 (q, J = 269.2Hz), 115.94 (q, J = 33.8Hz), 72.95, 50.66, 28.92, 24.38, 24.32, 24.23.

[0114] 19 F NMR (376MHz,CDCl3)δ-63.67.

[0115] Preparation Example 16

[0116] To a 10 mL reaction tube, 0.3 mmol of 2-(pyridin-4-yl)but-3-yn-2-ol, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-5,5,5-trifluoro-2-(pyridin-4-yl)pent-3-en-2-ol was isolated by column chromatography as a brown solid in a 94% yield.

[0117] 1 H NMR (400MHz, CDCl3) δ8.43(d,J=5.3Hz,2H),7.39(d,J=5.2Hz,2H),6.58(dq,J=15.6,1.7,1.3Hz,1H),6.01(dqd,J=15.7,6.4,1.1Hz,1H),1.68(s,3H).

[0118] 13 C NMR (101MHz, CDCl3) δ154.70, 149.25, 144.60 (q, J = 6.1Hz), 123.15 (q, J = 269.5Hz), 120.45, 117.23 (q, J = 34.0Hz), 72.49, 28.90.

[0119] 19 F NMR (376 MHz, CDCl3) δ-63.90.

[0120] Preparation Example 17

[0121] To a 10 mL reaction tube, 0.3 mmol of 1-cyclopentyl-1-phenylpropyl-2-yn-1-ol, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-1-cyclopentyl-4,4,4-trifluoro-1-phenylbut-2-en-1-ol was isolated by column chromatography as an orange liquid in a 59% yield.

[0122] 1 H NMR (400MHz, CDCl3) δ7.47–7.41(m,2H),7.36(dd,J=8.6,6.8Hz,2H),7.30–7.21(m,1H),6.69(dq,J=15.5,2.1H z,1H),5.98(dq,J=15.6,6.6Hz,1H),2.59(p,J=8.8Hz,1H),1.94(s,1H),1.64–1.39(m,7H),1.35–1.18(m,1H).

[0123] 13 C NMR (101MHz, CDCl3) δ144.74 (q, J = 6.0Hz), 144.11, 128.50, 127.32, 125.26, 123.5 3(q,J=269.4Hz),116.51(q,J=33.9Hz),77.43,48.62,27.03,26.84,26.08,25.87.

[0124] 19 F NMR (376MHz,CDCl3)δ-63.47.

[0125] Preparation Example 18

[0126] To a 10 mL reaction tube, 0.3 mmol of 1-cyclopropyl-1-phenylpropyl-2-yn-1-ol, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-1-cyclopropyl-4,4,4-trifluoro-1-phenylbut-2-en-1-ol was isolated by column chromatography as a yellow liquid in an 82% yield.

[0127] 1H NMR (400MHz, CDCl3) δ7.59–7.50(m,2H),7.43–7.36(m,2H),7.35–7.29(m,1H),6.53(dq,J=15.6,2.1Hz,1H), 6.05(dq,J=15.6,6.6Hz,1H),1.87(s,1H),1.38(tt,J=8.3,5.4Hz,1H),0.69–0.58(m,2H),0.55–0.44(m,2H).

[0128] 13 C NMR (101MHz, CDCl3) δ143.65, 143.58 (q, J = 6.0Hz), 128.52, 127.91, 125.88, 123.44 (q, J = 269.3Hz), 117.23 (q, J = 33.8Hz), 74.67, 20.51, 1.62, 1.17.

[0129] 19 F NMR (376MHz,CDCl3)δ-63.55.

[0130] Preparation Example 19

[0131] To a 10 mL reaction tube, 0.3 mmol of 1,1-bis(4-methoxyphenyl)-2-propyn-1-ol, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-4,4,4-trifluoro-1,1-bis(4-methoxyphenyl)but-2-en-1-ol was isolated by column chromatography as a yellow liquid in a 61% yield.

[0132] 1 H NMR (400MHz, CDCl3) δ7.23(d,J=8.4Hz,4H),6.94–6.87(m,1H),6.86(d,J=8.7Hz,4H),6.05(dq,J=15.3,6.6Hz,1H),3.79(s,6H),2.39(s,1H).

[0133] 13C NMR (101MHz, CDCl3) δ159.11, 144.81 (q, J = 6.0Hz), 136.42, 128.03, 123.54 (q, J = 269.5Hz), 116.67 (q, J = 33.8Hz), 113.76, 77.67, 55.26.

[0134] 19 F NMR (376MHz,CDCl3)δ-63.32.

[0135] Preparation Example 20

[0136] To a 10 mL reaction tube, 0.3 mmol of 1,1-bis(4-butoxyphenyl)-2-propyn-1-ol, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-1,1-bis(4-butoxyphenyl)-4,4,4-trifluorobut-2-en-1-ol was isolated by column chromatography as a brown liquid with a yield of 58% (E / Z = 3:1).

[0137] 1 H NMR(400MHz, CDCl3) δ7.22(d,J=8.7Hz,4H),6.94–6.88(m,1H),6.87(d,J=8.8Hz,4H),6.06(dq,J=15.7,6.6Hz, 1H),3.96(t,J=6.5Hz,4H),2.34(s,1H),1.77(dq,J=8.4,6.5Hz,4H),1.58–1.38(m,4H),0.99(t,J=7.4Hz,6H).

[0138] 13 C NMR(101MHz, CDCl3)δ158.73,144.90(q,J=6.1Hz),136.22,128.00,123.58(q, J=269.5Hz),116.59(q,J=33.7Hz),114.29,77.72,67.71,31.25,19.21,13.80.

[0139] 19 F NMR (376 MHz, CDCl3) δ-63.31.

[0140] Preparation Example 21

[0141] To a 10 mL reaction tube, 0.3 mmol of propargyl benzoate, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-4,4,4-trifluorobut-2-en-1-yl benzoate was isolated by column chromatography as a colorless liquid in a 62% yield.

[0142] 1 H NMR (400MHz, CDCl3) δ8.08(d,J=7.5Hz,2H),7.61(t,J=7.4Hz,1H),7.48(t,J=7.7Hz,2 H),6.56(ddq,J=15.8,4.5,2.2Hz,1H),6.05–5.81(m,1H),4.96(dp,J=5.0,2.6Hz,2H).

[0143] 13 C NMR (101MHz, CDCl3) δ 165.73, 134.08 (q, J = 6.6Hz), 133.46, 129.71, 129.35, 128.55, 122.64 (q, J = 269.3Hz), 119.89 (q, J = 34.4Hz), 62.14.

[0144] 19 F NMR (376MHz,CDCl3)δ-64.51.

[0145] Preparation Example 22

[0146] To a 10 mL reaction tube, 0.3 mmol of propargyl 4-methoxybenzoate, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-4,4,4-trifluorobut-2-en-1-yl-4-methoxybenzoate was isolated by column chromatography as a colorless liquid in a 73% yield.

[0147] 1H NMR (400MHz, CDCl3) δ8.03(d,J=8.6Hz,2H),6.95(d,J=8.7Hz,2H),6.55(ddq,J=15.7,4 .5, 2.4Hz, 1H), 5.96 (dq, J=15.3, 6.4Hz, 1H), 4.92 (dp, J=5.1, 2.6Hz, 2H), 3.87 (s, 3H).

[0148] 13 C NMR (101MHz, CDCl3) δ165.43, 163.73, 134.35 (q, J = 6.5Hz), 131.77, 122.68 (q, J = 269.3Hz), 121.66, 119.62 (q, J = 34.3Hz), 113.78, 61.85, 55.45.

[0149] 19 F NMR (376MHz,CDCl3)δ-64.46.

[0150] Preparation Example 23

[0151] To a 10 mL reaction tube, 0.3 mmol of 3-chloro-5-ethynylpyridine, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-3-chloro-5-(3,3,3-trifluoropropyl-1-en-1-yl)pyridine was isolated by column chromatography as a colorless liquid in a 75% yield.

[0152] 1 H NMR (400MHz, CDCl3) δ8.57(dd,J=6.9,2.1Hz,2H),7.78(t,J=2.2Hz,1H),7.13(dq,J=16.2,2.2Hz,1H),6.31(dq,J=16.2,6.3Hz,1H).

[0153] 13 C NMR (101MHz, CDCl3) δ149.78, 146.83, 133.44, 132.97 (q, J = 6.8Hz), 132.52, 130.32, 119.57 (q, J = 34.8Hz).

[0154] 19 F NMR (376 MHz, CDCl3) δ-64.04.

[0155] Preparation Example 24

[0156] To a 10 mL reaction tube, 0.3 mmol of 1-Boc-4-ethynylpiperidine, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. Column chromatography was performed to obtain tert-butyl (E)-4-(3,3,3-trifluoropropyl-1-en-1-yl)piperidine-1-carboxylate as a light green liquid in a 61% yield.

[0157] 1 H NMR (400MHz, CDCl3) δ6.30 (ddq, J=15.9, 6.5, 2.1Hz, 1H), 5.58 (dqd, J=16.0, 6.3, 1.5Hz, 1H), 4.12 (s, 2H) ,3.05–2.52(m,2H),2.34–2.08(m,1H),1.70(d,J=12.1Hz,2H),1.44(s,9H),1.30(qd,J=12.3,4.4Hz,2H).

[0158] 13 C NMR (101MHz, CDCl3) δ154.66, 143.59 (q, J = 6.3Hz), 123.10 (q, J = 269.2Hz), 117.29 (q, J = 33.5Hz), 79.57, 43.33, 37.90, 30.54, 28.37.

[0159] 19 F NMR (376 MHz, CDCl3) δ-64.00.

[0160] Preparation Example 25

[0161] To a 10 mL reaction tube, 0.3 mmol of 2,7-dibromo-9-(prop-2-yn-1-yl)-9H-carbazole, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-2,7-dibromo-9-(4,4,4-trifluorobut-2-en-1-yl)-9H-carbazole was isolated by column chromatography as a pale yellow solid in a 46% yield.

[0162] 1H NMR (400MHz, CDCl3) δ7.89(d,J=8.2Hz,2H),7.43(d,J=1.6Hz,2H),7.39(dd,J=8.3,1.7Hz,2 H),6.56(ddq,J=15.8,4.2,2.1Hz,1H),5.79–5.13(m,1H),4.90(ddd,J=6.9,4.3,2.5Hz,2H).

[0163] 13 C NMR (101MHz, CDCl3) δ140.85, 133.67 (q, J = 6.1Hz), 123.53, 122.40 (q, J = 269.7Hz), 121.69, 121.53, 120.34 (q, J = 34.5Hz), 120.14, 111.73, 43.05.

[0164] 19 F NMR (376 MHz, CDCl3) δ-64.01.

[0165] Preparation Example 26

[0166] To a 10 mL reaction tube, 0.3 mmol of pyran, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. Column chromatography separated the two products, respectively, to afford (E)-2-((4,4,4-trifluorobut-2-en-1-yl)oxy)tetrahydro-2H-pyran as a colorless liquid in 51% yield, and (Z)-2-((4,4,4-trifluorobut-2-en-1-yl)oxy)tetrahydro-2H-pyran as a colorless liquid in 42% yield.

[0167] (E)-2-((4,4,4-Trifluorobut-2-en-1-yl)oxy)tetrahydro-2H-pyran

[0168] 1 H NMR (400MHz, CDCl3) δ6.45 (dqd, J=15.7, 4.2, 2.1Hz, 1H), 5.94 (dqt, J=15.3, 6.5, 2.2Hz, 1H), 4.66 (t, J=3.5Hz, 1H) ,4.44–4.30(m,1H),4.13–3.99(m,1H),3.90–3.73(m,1H),3.63–3.37(m,1H),1.88–1.69(m,2H),1.68–1.47(m,4H).

[0169] 13 C NMR (101MHz, CDCl3) δ 136.66 (q, J = 6.3Hz), 123.12 (q, J = 269.1Hz), 118.28 (q, J = 33.9Hz), 98.26, 64.68, 62.09, 30.32, 25.29, 19.13.

[0170] 19 F NMR (376 MHz, CDCl3) δ-64.22.

[0171] (Z)-2-((4,4,4-Trifluorobut-2-en-1-yl)oxy)tetrahydro-2H-pyran

[0172] 1 H NMR (400MHz, CDCl3) δ6.18(dt,J=11.8,5.8Hz,1H),5.79–5.49(m,1H),4.63(dd,J=4.2,2.8Hz,1H),4.49(ddt,J=14.8,5.3,2.6Hz,1H),4.30 (ddt,J=14.8,6.2,2.6Hz,1H),3.85(ddd,J=11.2,8.0,3.3Hz,1H),3.52(ddd,J=8.8,6.4,3.9Hz,1H),1.88–1.69(m,2H),1.60–1.48(m,4H).

[0173] 13 C NMR (101MHz, CDCl3) δ 139.88 (q, J = 4.9Hz), 122.88 (q, J = 271.5Hz), 118.42 (q, J = 34.6Hz), 98.69, 63.26 (d, J = 2.2Hz), 62.33, 30.48, 25.30, 19.34.

[0174] 19 F NMR (376 MHz, CDCl3) δ-59.17.

[0175] Preparation Example 27

[0176] To a 10 mL reaction tube, 0.3 mmol of N-(prop-2-yn-1-yl)cyclohexanecarboxamide, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. Column chromatography separation afforded (E)-N-(4,4,4-trifluorobut-2-en-1-yl)cyclohexanecarboxamide as a white solid in 44% yield, and (Z)-N-(4,4,4-trifluorobut-2-en-1-yl)cyclohexanecarboxamide as a white solid in 32% yield.

[0177] (E)-N-(4,4,4-Trifluorobut-2-en-1-yl)cyclohexanecarboxamide

[0178] 1 H NMR (400MHz, CDCl3) δ6.35 (dqd, J=14.8, 4.6, 2.3Hz, 1H), 5.94 (s, 1H), 5.69 (dq, J=15.3, 6.3Hz, 1H), 3.98 (tp, J=5.1, 2. 4Hz,2H),2.13(tt,J=11.8,3.5Hz,1H),1.90–1.73(m,4H),1.44(qd,J=12.0,3.2Hz,2H),1.25(tt,J=16.1,10.5Hz,4H).

[0179] 13 C NMR (101MHz, CDCl3) δ176.22, 136.77 (q, J = 6.3Hz), 122.78 (q, J = 269.4Hz), 118.98 (q, J = 34.1Hz), 45.35, 39.12, 29.65, 25.61.

[0180] 19 F NMR (376 MHz, CDCl3) δ-64.12.

[0181] (Z)-N-(4,4,4-Trifluorobut-2-en-1-yl)cyclohexanecarboxamide

[0182] 1H NMR (400MHz, CDCl3) δ6.00(dq,J=11.7,6.8Hz,1H),5.80(s,1H),5.67(dq,J=10.9,8.7Hz,1H),4.10(tt,J=6.4 ,2.1Hz,2H),2.09(tt,J=11.8,3.4Hz,1H),1.89–1.70(m,4H),1.42(qd,J=12.0,3.1Hz,2H),1.33–1.16(m,4H).

[0183] 13 C NMR (101MHz, CDCl3) δ176.18, 139.18 (q, J = 5.1Hz), 122.85 (q, J = 271.8Hz), 119.65 (q, J = 34.4Hz), 45.27, 36.65 (d, J = 1.7Hz), 29.56, 25.63.

[0184] 19 F NMR (376MHz,CDCl3)δ-58.43.

[0185] Preparation Example 28

[0186] To a 10 mL reaction tube, 0.3 mmol of 4-methoxy-N-(prop-2-yn-1-yl)benzamide, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. Column chromatography separation afforded (E)-4-methoxy-N-(4,4,4-trifluorobut-2-en-1-yl)benzamide as a yellow solid in 48% yield, and (Z)-4-methoxy-N-(4,4,4-trifluorobut-2-en-1-yl)benzamide as a yellow solid in 41% yield.

[0187] (E)-4-Methoxy-N-(4,4,4-trifluorobut-2-en-1-yl)benzamide

[0188] 1 H NMR (400MHz, CDCl3) δ7.76 (d, J = 8.7Hz, 2H), 6.91 (d, J = 8.7Hz, 2H), 6.58 (s, 1H), 6.44 (dd q,J=15.7,5.1,2.5Hz,1H),5.84–5.64(m,1H),4.16(tt,J=5.4,2.6Hz,2H),3.84(s,3H).

[0189] 13 C NMR (101MHz, CDCl3) δ167.05, 162.46, 136.67 (q, J = 6.3Hz), 128.82, 125.88, 122.79 (q, J = 269.3Hz), 119.24 (q, J = 34.0Hz), 113.82, 55.39, 39.85.

[0190] 19 F NMR (376 MHz, CDCl3) δ-64.07.

[0191] (Z)-4-Methoxy-N-(4,4,4-trifluorobut-2-en-1-yl)benzamide

[0192] 1 H NMR (400MHz, CDCl3) δ7.74(d,J=8.7Hz,2H),6.90(d,J=8.7Hz,2H),6.58(s,1H),6.11(dq ,J=11.3,6.6Hz,1H),5.77–5.58(m,1H),4.28(ddt,J=8.8,6.0,2.3Hz,2H),3.83(s,3H).

[0193] 13 C NMR (101MHz, CDCl3) δ167.16, 162.37, 139.17 (q, J = 5.0Hz), 128.78, 126.03, 12 2.88(q,J=272.1Hz),119.61(q,J=34.2Hz),113.77,55.36,37.32(d,J=2.0Hz).

[0194] 19 F NMR (376 MHz, CDCl3) δ-58.44.

[0195] Preparation Example 29

[0196] To a 10 mL reaction tube, 0.3 mmol of N-(prop-2-yn-1-yl)-4-(trifluoromethyl)benzamide, 0.9 mmol of sodium trifluoromethylsulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. Column chromatography separation afforded (E)-N-(4,4,4-trifluorobut-2-en-1-yl)-4-(trifluoromethyl)benzamide as a white solid in 46% yield, and (Z)-N-(4,4,4-trifluorobut-2-en-1-yl)-4-(trifluoromethyl)benzamide as a white solid in 39% yield.

[0197] (E)-N-(4,4,4-Trifluorobut-2-en-1-yl)-4-(trifluoromethyl)benzamide

[0198] 1 H NMR(400MHz, CDCl3) δ7.89(d,J=8.0Hz,2H),7.68(d,J=8.0Hz,2H),6.87(s,1H),6.44(dqd ,J=18.2,5.3,2.1Hz,1H),5.78(dqd,J=14.3,6.3,1.6Hz,1H),4.19(td,J=5.4,2.5Hz,2H).

[0199] 13 C NMR (101MHz, CDCl3) 166.38, 136.94, 135.92 (q, J = 6.3Hz), 133.59 (q, J = 32.8Hz), 127.49, 125. 69(q,J=3.7Hz), 123.51(q,J=272.6Hz), 122.63(d,J=269.4Hz), 119.74(q,J=34.2Hz), 40.07.

[0200] 19 F NMR (376MHz, CDCl3) δ-63.06,-64.24.

[0201] (Z)-N-(4,4,4-Trifluorobut-2-en-1-yl)-4-(trifluoromethyl)benzamide

[0202] 1H NMR(400MHz, CDCl3) δ7.87(d,J=8.1Hz,2H),7.68(d,J=8.0Hz,2H),6.73(s,1H),6.12 (dqd,J=13.4,6.8,1.5Hz,1H),5.89–5.63(m,1H),4.32(ddt,J=6.5,4.4,2.1Hz,2H).

[0203] 13 C NMR (101MHz, CDCl3) δ166.43,138.21(q,J=5.1Hz),137.05,133.52(q,J=32.7Hz),127.45,125.68(q, J=3.7Hz), 123.53 (q, J=272.5Hz), 122.78 (d, J=272.0Hz), 120.29 (q, J=34.3Hz), 37.48 (d, J=1.5Hz).

[0204] 19 F NMR (376MHz, CDCl3) δ-58.49,-63.05.

[0205] Preparation Example 30

[0206] To a 10 mL reaction tube, 0.3 mmol of ethinylgestrel, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The mixture was irradiated with 450-465 nm blue light at room temperature for 12 hours. Column chromatography separated the product to afford (8R,9S,10R,13S,14S,17R)-17-hydroxy-10,13-dimethyl-17-((E)-3,3,3-trifluoropropyl-1-en-1-yl)-1,2,6,7,8,9,10,11,12,14,15,16,17-tetradecahydro-3H-cyclopenta[a]phenanthrene-3-one as a white solid in 83% yield.

[0207] 1 H NMR (400MHz, CDCl3) δ6.51 (dq, J=15.6, 2.1Hz, 1H), 5.87 (dq, J=15.6, 6.5Hz, 1H), 5.72 (s, 1H), 2.4 9–2.21(m,4H),2.10–1.80(m,6H),1.78–1.36(m,8H),1.18(s,3H),1.12–1.00(m,2H),0.96(s,3H).

[0208] 13 C NMR (101MHz, CDCl3) δ199.57, 170.98, 144.28 (q, J = 6.0Hz), 123.89, 123.55 (q, J = 269.2Hz), 115.92 (q, J = 33.5Hz), 83.03,53.34,50.21,46.91,38.55,37.18,36.25,35.55,33.83,32.65,32.20,31.51,23.57,20.52,17.32,13.98.

[0209] 19 F NMR (376 MHz, CDCl3) δ-63.14.

[0210] Preparation Example 31

[0211] To a 10 mL reaction tube, 0.3 mmol of norethindrone, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The mixture was irradiated with 450-465 nm blue light at room temperature for 12 hours. Column chromatography revealed (8R,9S,10R,13S,14S,17R)-17-hydroxy-13-methyl-17-((E)-3,3,3-trifluoropropyl-1-en-1-yl)-1,2,6,7,8,9,11,12,13,14,15,16,17-tetradecahydro-3H-cyclopenta[a]phenanthrene-3-one as a white solid in a 71% yield.

[0212] 1 H NMR (400MHz, CDCl3) δ6.51(dq,J=15.6,2.1Hz,1H),5.87(dq,J=15.8,6.6Hz,1H),5.81(s,1H),2.47(ddd,J=14.7,4.1,2.5Hz,1H),2.39(dt,J=1 5.1,3.8Hz,1H),2.23(ddt,J=19.6,12.9,3.8Hz,4H),1.99–1.79(m,5H) ,1.62–1.38(m,4H),1.38–1.18(m,3H),1.14–1.04(m,2H),0.97(s,3H).

[0213] 13C NMR (101MHz, CDCl3) δ200.04, 166.52, 144.34 (q, J = 6.0Hz), 124.57, 123.55 (q, J = 269.3Hz), 115.91 (q, J = 33.4H z),83.03,49.46,49.02,47.08,42.40,40.97,37.10,36.39,35.31,32.15,30.64,26.44,25.92,23.39,13.99.

[0214] 19 F NMR (376 MHz, CDCl3) δ-63.13.

[0215] Preparation Example 32

[0216] To a 10 mL reaction tube, 0.3 mmol of propynyl isoxalate, 0.9 mmol of sodium trifluoromethylsulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. (E)-4,4,4-trifluorobut-2-en-1-yl-2-(10-oxo-10,11-dihydrodibenzo[b,f]oxolan-2-yl)acetate was isolated by column chromatography as a brown solid in a 44% yield.

[0217] 1 H NMR (400MHz, CDCl3) δ8.14(s,1H),7.88(d,J=7.7Hz,1H),7.56(t,J=7.5Hz,1H),7.48(d,J=7.7Hz,1H),7.47–7.39(m,1H),7.36(d,J=7.5Hz ,1H),7.05(d,J=8.4Hz,1H),6.41(dqd,J=15.9,4.5,2.2Hz,1H),5.96–5.65(m,1H),5.19(s,2H),4.72(dq,J=4.6,2.2Hz,2H),3.71(s,2H).

[0218] 13C NMR (101MHz, CDCl3) δ190.74,170.56,160.59,140.32,136.18,135.45,133.63(q,J=6.6Hz),132.81,132.47,129 .44,129.26,127.80,127.11,125.20(q,J=269.5Hz),125.14,121.20,119.92(q,J=34.4Hz),73.59,62.09,39.91.

[0219] 19 F NMR (376MHz,CDCl3)δ-64.57.

[0220] Preparation Example 33

[0221] To a 10 mL reaction tube, 0.3 mmol of clodinafop-propargyl, 0.9 mmol of sodium trifluoromethanesulfinate, 1 mol% of 3DPA2FBN, and 0.9 mmol of water were added. 3.0 mL of a 2:1 mixture of dimethyl sulfoxide and N,N-dimethylformamide was added as the solvent. The reaction was allowed to proceed at room temperature under 450-465 nm blue light irradiation for 12 hours. Column chromatography separated the product to give (E)-4,4,4-trifluorobut-2-en-1-yl-2-(4-((5-chloro-3-fluoropyridin-2-yl)oxy)phenoxy)propanoate as a yellow liquid in a 43% yield.

[0222] 1 H NMR(400MHz, CDCl3)δ7.86(d,J=2.2Hz,1H),7.49(dd,J=9.1,2.2Hz,1H),7.15–7.01(m,2H),6.94–6.88(m,2H),6.40(ddq ,J=15.7,4.3,2.2Hz,1H),5.89–5.68(m,1H),4.86–4.80(m,1H),4.78(ddt,J=7.1,4.8,2.5Hz,2H),1.66(d,J=6.7Hz,3H).

[0223] 13 C NMR (101MHz, CDCl3) δ171.35, 154.70, 151.25 (d, J = 11.4Hz), 147.24, 146.97 (d, J = 265.9Hz), 140.13 (d, J = 6.0 Hz), 133.14 (q, J = 6.4Hz), 124.95 (d, J = 17.9Hz), 122.37, 120.42 (d, J = 34.5Hz), 116.05, 73.00, 62.32, 18.62.

[0224] 19 F NMR(376MHz,CDCl3)δ-64.69,-134.33.

Claims

1. A method for blue light-induced trifluoromethylation of alkynyl compounds, characterized in that: Contains C vinyl The synthesis method of the alkenyl compound III having a -CF3 bond is as follows: Using alkynyl compound I and sodium trifluoromethylsulfinate II as raw materials, in the presence of photocatalyst 3DPA2FBN and water, a mixed solution of dimethyl sulfoxide and N,N-dimethylformamide as solvent, sodium trifluoromethylsulfinate as the trifluoromethyl source, and blue light irradiation at room temperature, the alkynyl group is subjected to a hydrotrifluoromethylation reaction to obtain a C-containing vinyl -CF3 bond alkenyl compound III; Where R is H, C 10 Straight-chain alkyl, 1-methyl-1-hydroxybenzyl, 4-methoxyphenyl or trimethylsilyl; R' is H, C 10 straight-chain alkyl, 1-methyl-1-hydroxybenzyl, 4-methoxyphenyl or trimethylsilyl; The molar amount of the sodium trifluoromethanesulfinate is 1.5 to 3 times the molar amount of the alkynyl compound.

2. The method for blue light-induced trifluoromethylation of alkynyl compounds according to claim 1, characterized in that: The molar amount of the 3DPA2FBN is 0.5-1% of the molar amount of the alkynyl compound; The molar amount of the water is 3 to 5 times the molar amount of the alkynyl compound.

3. The method for blue light-induced trifluoromethylation of alkynyl compounds according to claim 1, characterized in that: The ratio of the mixed solution is dimethyl sulfoxide / N,N-dimethylformamide is 2:1~4:

1.

4. The method for blue light-induced trifluoromethylation of an alkynyl compound according to any one of claims 1 to 3, characterized in that: The reaction conditions are: at room temperature, irradiated by a 24-26 W blue light lamp, and reacted for 8-12 hours.

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