A method for synthesizing fluoroalkyl substituted pyrrolidine

Abstract

The present application discloses a method for synthesizing fluoroalkyl-substituted pyrrolidines in the field of organic synthesis technology, which uses easily available N, N-diallylamine and fluoroalkyl iodide as raw materials, and innovatively adopts a solvent-free method under visible light irradiation to obtain a variety of fluoroalkylated pyrrolidines and their derivatives in high yield. The reaction does not require additional additives for most substrates, and unreacted raw materials can also be recovered during post-treatment. Therefore, the method has a simple system, good atom economy, excellent functional group compatibility, and high stereoselectivity.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for synthesizing fluoroalkyl-substituted pyrrolidine. Background Art

[0002] Due to the special properties of fluorine, fluorinated organic compounds have a wide range of applications in life sciences, biomedicine, and materials science. For example, Chin. Chem. Lett., 2021, 32(11), 3342-3354; Chem. Rev, 2016, 116(2), 422-518; Chem. Rev, 2014, 114(4), 2432-2506; Chem. Rev, 2016, 116(2), 719-766. Driven by these industries, chemists have developed a variety of synthetic methodologies to synthesize various fluorinated organic compounds.

[0003] Pyrrolidine is one of the most common nitrogen-containing heterocycles in drug molecules (Eur. J. Med. Chem., 2022, 235, 114303; J. Med. Chem., 2000, 43 (23), 4452–4464; J. Med. Chem., 2021, 64 (20), 15313–15333). However, the methods for obtaining fluoroalkylated pyrrolidines are still very limited, and transition metal catalysts are necessary (Adv. Synth. Catal., 2018, 360 (3), 562–567; Angew. Chem. Ind. Ed., 2019, 58 (46), 16637–16643).

[0004]

[0005] However, this strategy still has several problems to be solved, such as (1) the need to use expensive metal catalysts such as Ru, Pd, Cu, Fe, etc.; (2) some catalytic systems need to be used in conjunction with expensive N and P ligands. Summary of the invention

[0006] In view of the shortcomings of the prior art, the present invention designs an amine to play all the roles of substrate, electron donor compound and base, and innovatively develops a method for synthesizing fluoroalkylated pyrrolidine using N,N-diallylamine compounds as substrates and electron donor compounds and fluoroalkyl iodides.

[0007] One of the purposes of the present invention is to provide a method for synthesizing a fluoroalkyl-substituted pyrrolidine, characterized in that the method comprises the steps of: reacting a compound of formula A with a compound of formula B in an inert gas under visible light irradiation to form a compound of formula C;

[0008]

[0009] In the above reaction formula, R is optionally phenyl, C 1-15 Alkyl-substituted phenyl, C 1-15 Alkoxy-substituted phenyl, halogen-substituted phenyl, cyano-substituted phenyl, halogenated phenyl, ester-substituted phenyl, pyrimidine, quinoline, pyridine, halogen-substituted pyridine, methyl phenylpropionate, ethyl phenylpropionate, tert-butyl phenylpropionate, methyl 3-(4-nitrophenyl)propionate, methyl 3-(4-chlorophenyl)propionate, methyl 6-((tert-butoxycarbonyl)amino)hexanoate, methyl 3-hydroxypropionate, methyl 3-(benzyloxy)propionate or indane.

[0010] In a preferred embodiment, the molar ratio of the compound of formula A to the compound of formula B is 1 to 3:1, and more preferably 2:1.

[0011] In another preferred embodiment, the reaction is carried out at 0-50°C, preferably at 20-40°C, and more preferably at 25°C.

[0012] In another preferred embodiment, the inert gas is selected from: nitrogen or argon.

[0013] In another preferred embodiment, the reaction is carried out under visible light irradiation, preferably the visible light is blue light or violet light, more preferably blue light.

[0014] In another preferred embodiment, an additive base is added during the reaction. The additive base is selected from carbonates, and more preferably potassium carbonate.

[0015] The present invention also provides some new compounds, which are compounds C-1 to C-36, and the structural formulas of the above compounds are:

[0016]

[0017] The above compounds have potential applications in medicine, pesticides or materials.

[0018] Through long-term and in-depth research, the inventors have discovered a new method for fluoroalkylation of N,N-diallylamine compounds, which uses N,N-diallylamine compounds as substrates, bases and electron donor compounds and fluoroalkyl iodides to synthesize fluoroalkyl-substituted pyrrolidines in an inert gas under visible light irradiation. At the same time, the system has excellent functional group compatibility, simplicity of synthesis, atom economy, and suitability for large-scale production.

[0019] The beneficial effects of the present invention are as follows: (1) The raw materials used in this method are all from cheap industrial raw materials, and light is used to promote the reaction, and the reaction can proceed smoothly without any additives. It is economical, green, and environmentally friendly and suitable for large-scale production. (2) The reaction has excellent functional group compatibility and reaction diversity. Some substrates that are difficult to synthesize using conventional methods can be efficiently synthesized using this method. (3) This method can be directly used for the synthesis of fluorine-containing amino acids, and these structures have very important applications in the field of biomedicine.

[0020] It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described below (such as embodiments) can be combined with each other to form a new or preferred technical solution. Due to space limitations, they will not be described one by one here.

[0021] Terminology: As used herein, the term "C 1-15 The term "alkyl" refers to a straight or branched chain alkyl group having 1 to 15 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or the like.

[0022] The term "C 1-15 The term "alkoxy" refers to a straight or branched alkoxy group having 1 to 15 carbon atoms, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy or the like.

[0023] The term "halogen" refers to fluorine, chlorine, bromine or iodine.

[0024] The term "halogenated" refers to a group in which the H is replaced by one or more halogen atoms which may be the same or different, such as trifluoromethyl, pentafluoroethyl, trifluoromethoxy, difluorovinyl or similar groups. DETAILED DESCRIPTION

[0025] The following is further described in detail through specific implementation methods:

[0026] The present invention will be further described below in conjunction with specific implementation. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples without specifying specific conditions are usually based on conventional conditions or the conditions recommended by the manufacturer. Unless otherwise stated, percentages and parts are calculated by weight.

[0027] The present invention provides a method for synthesizing a fluoroalkyl-substituted pyrrolidine, comprising the steps of: reacting a compound of formula A (N,N-diallylamine compound) as a substrate and an electron donor compound with a compound of formula B (fluoroalkyl iodide) in an inert gas at a certain temperature (unlimited, the reaction temperature in the embodiment is 25° C.) under irradiation with visible light, thereby forming a compound of formula C. Considering that the substitution of the electron-withdrawing group may reduce the N-nucleophilicity of the aniline, an additional additive base may be used to promote the conversion.

[0028]

[0029] In the above reaction formula, R is as defined above.

[0030] The above reaction can also be carried out in the presence of an additive, wherein the additive base is potassium carbonate.

[0031] The compound of formula A is selected from the group consisting of:

[0032]

[0033] Wherein, the compound of formula B is preferably a compound selected from the following group:

[0034] B-1: ICF2CO2Et; B-2: IC4F9.

[0035] The compounds of formula A and formula B of the present invention can be prepared by commercially available methods or methods well known to those skilled in the art to which the present invention belongs. However, the specific conditions of the method, such as reactants, solvents, amounts of compounds used, reaction temperature, time required for reaction, etc., are not limited to the following explanation.

[0036] The compound of formula C prepared by the present invention can be further modified as needed to prepare various functional compounds.

[0037] The product obtained by the preparation method of the present invention can be separated and purified by a variety of methods, including recrystallization, column chromatography, etc. The above purification methods are all conventional methods in the art. For example, when performing recrystallization, a mixed solvent of a polar solvent and a non-polar solvent can be used, preferably a mixed solvent such as ethyl acetate-petroleum ether, ethanol-petroleum ether, etc. When using column chromatography, the developing solvent used can be a single solvent or a mixed solvent, such as petroleum ether or a mixed solvent of ethyl acetate-petroleum ether, etc.

[0038] The above features mentioned in the present invention or the features mentioned in the embodiments can be combined in any way. All the features disclosed in the specification of this case can be used in any combination form, and each feature disclosed in the specification can be replaced by any alternative feature that provides the same, equal or similar purpose. Therefore, unless otherwise specified, the disclosed features are only general examples of equal or similar features.

[0039] In the following examples, conventional post-treatment methods in the art were used for purification.

[0040] Examples 1-3

[0041] Table 1. Yields of C-1 compounds at different wavelengths

[0042]

[0043]

[0044] 104.0 mg (0.6 mmol) of compound A-1 and 75.0 mg (0.3 mmol) of compound B-1 were injected into a 25 mL quartz reaction tube after argon replacement for 5 times, and irradiated with blue light of each wavelength in the above table for 12 hours to obtain compound C-1. The yield is shown in the table (fluorine spectrum yield, (the ratio of trans: cis in brackets)). Trans: 1 H NMR (400MHz, CDCl3) δ7.26(t,J=7.8Hz,2H),6.73(t,J=7.4Hz,1H),6.58(d,J=8.0Hz,2H),4.36(q,J=7.2Hz,2H),3.53–3.40(m,3H),3.34 –3.26(m,2H),3.12(t,J=10.2Hz,1H),2.88–2.80(m,1H),2.73–2.64(m,1H),2.41–2.27(m,1H),2.24–2.10(m,1H),1.38(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-104.07 (ddd, J=261.5Hz, 21.8Hz, 11.7Hz, 1F), -106.02 (ddd, J=261.5Hz, 21.1Hz, 14.3Hz, 1F). 13 C NMR (101 MHz, CDCl3) δ 163.9 (t, J = 32.7 Hz), 147.2, 129.2, 116.4, 115.7 (t, J = 253.0 Hz), 111.6, 63.2, 53.2, 51.5, 44.8, 35.7 (t, J = 2.8 Hz), 32.8 (t, J = 23.3 Hz), 14.0, 4.3. C-1 is a new compound.

[0045] Example 4

[0046]

[0047] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 104.0 mg (0.6 mmol) of compound A-1 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-1 was obtained with a yield of 81% (dr = 2.1:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ7.26(t,J=7.8Hz,2H),6.73(t,J=7.4Hz,1H),6.58(d,J=8.0Hz,2H),4.36(q,J=7.2Hz,2H),3.53–3.40(m,3H),3.34 –3.26(m,2H),3.12(t,J=10.2Hz,1H),2.88–2.80(m,1H),2.73–2.64(m,1H),2.41–2.27(m,1H),2.24–2.10(m,1H),1.38(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-104.07 (ddd, J=261.5Hz, 21.8Hz, 11.7Hz, 1F), -106.02 (ddd, J=261.5Hz, 21.1Hz, 14.3Hz, 1F). 13 CNMR (101 MHz, CDCl3) δ163.9 (t, J = 32.7 Hz), 147.2, 129.2, 116.4, 115.7 (t, J = 253.0 Hz), 111.6, 63.2, 53.2, 51.5, 44.8, 35.7 (t, J = 2.8 Hz), 32.8 (t, J = 23.3 Hz), 14.0, 4.3. C-1 is a new compound.

[0048] Example 5

[0049]

[0050] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 104.0 mg (0.6 mmol) of compound A-1 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After stirring for 10 min under light-proof conditions, no compound C-1 was obtained after fluorine spectrum detection.

[0051] Example 6

[0052]

[0053] Into a 25 mL quartz reaction tube after argon replacement 55 times, 112.4 mg (0.6 mmol) of compound A-2 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-2 was obtained with a yield of 84% (dr = 2.2: 1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ7.07(d,J=8.0Hz,2H),6.55(br,2H),4.36(q,J=7.2Hz,2H),3.53–3.38(m,3H),3.33–2.25(m,2H),3.13(t, J=10.2Hz,1H),2.88–2.80(m,1H),2.76–2.65(m,1H),2.41–2.31(m,1H),2.27(s,3H),2.22–2.10(m,1H),1.38(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-104.07 (br.d, J=258.7Hz, 1F), -106.04 (dm, J=258.7Hz, 1F). 13 C NMR (101 MHz, CDCl3) δ 163.8 (t, J = 32.6 Hz), 144.7, 130.1, 129.8, 115.7 (t, J = 252.8 Hz), 112.3, 63.2, 54.0, 52.3, 44.6, 35.6 (t, J = 3.0 Hz), 32.7 (t, J = 23.3 Hz), 20.3, 14.0, 4.5. C-2 is a new compound.

[0054] Example 7

[0055]

[0056] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 120.8 mg (0.6 mmol) of compound A-3 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-3 was obtained with a yield of 88% (dr = 2.2:1). The ratio of trans: cis is in brackets. Trans: 1H NMR(400MHz, CDCl3)δ7.00(d,J=8.4Hz,1H),6.40(br.s,1H),6.35(br.d,J=7.6Hz,1 H),4.36(q,J=7.2Hz,2H),3.71(t,J=8.4Hz,1H),3.54(t,J=8.4Hz,1H),3.41(dd,J= 10.4Hz, 4.0Hz, 1H), 3.19 (t, J = 9.2Hz, 1H), 3.14–3.09 (m, 2H), 2.46–2.28 (m, 2H), 2. 24(s,3H),2.22–2.19(m,1H),2.17(s,3H),2.14–2.02(m,1H),1.38(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-103.26 (ddd, J=262.2Hz, 22.9Hz, 11.7Hz, 1F), -106.12 (ddd, J=262.2Hz, 21.8Hz, 16.5Hz, 1F). 13 C NMR (101 MHz, CDCl3) δ 163.8 (t, J = 26.1 Hz), 154.8, 145.2, 137.4, 130.3, 115.7 (t, J = 202.0 Hz), 113.5, 109.5, 63.2, 53.7, 52.0, 44.7, 35.6 (t, J = 2.4 Hz), 32.7 (t, J = 18.6 Hz), 20.2, 18.6, 14.0, 4.5. C-3 is a new compound.

[0057] Example 8

[0058]

[0059] Into a 25 mL quartz reaction tube replaced with argon five times, 120.8 mg (0.6 mmol) of compound A-4 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-4 was obtained with a yield of 88% (dr = 2.3: 1). The ratio of trans: cis is in brackets. Trans: 1H NMR (400MHz, CDCl3) δ7.09(d,J=7.6Hz,2H),6.51(d,J=7.6Hz,2H),4.36(q,J=7.2Hz,2H),3.50–3.38(m,3H),3.33–3.24(m,2H),3.11(t,J=10.0Hz,1 H),2.87–2.77(m,1H),2.71–2.62(m,1H),2.56(q,J=7.2Hz,2H),2.40–2.2 6(m,1H),2.23–2.09(m,1H),1.38(t,J=7.2Hz,3H),1.20(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-104.10 (dm, J=261.7Hz, 1F), -106.05 (ddd, J=261.7Hz, 23.7Hz, 15.8Hz, 1F). 13 C NMR (101 MHz, CDCl3) δ 163.9 (t, J = 32.7 Hz), 145.3, 132.1, 128.5, 115.7 (t, J = 252.7 Hz), 111.6, 63.2, 53.3, 51.6, 44.8, 35.6 (t, J = 2.9 Hz), 32.7 (t, J = 23.3 Hz), 27.8, 16.1, 14.0, 4.6. C-4 is a new compound.

[0060] Example 9

[0061]

[0062] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 137.6 mg (0.6 mmol) of compound A-5 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-5 was obtained with a yield of 91% (dr = 2.3:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ7.31(d,J=8.4Hz,2H),6.55(d,J=8.8Hz,2H),4.37(q,J=7.2Hz,2H),3.52–3.41(m,3H),3.34–3.27(m,2H),3.1 2(t,J=10.2Hz,1H),2.86–2.79(m,1H),2.71–2.62(m,1H),2.41–2.27(m,1H),2.25–2.10(m,1H),1.39(t,J=7.2Hz,3H),1.32(s,9H). 19F NMR (376MHz, CDCl3) δ-104.18 (ddd, J=261.1Hz, 21.8Hz, 12.0Hz, 1F), -106.14 (ddd, J=261.1Hz, 21.4Hz, 14.3Hz, 1F). 13 C NMR (101 MHz, CDCl3) δ 163.9 (t, J = 32.6 Hz), 145.0, 138.9, 126.0, 115.7 (t, J = 252.7 Hz), 111.2, 63.2, 53.1, 51.5, 44.9, 35.7 (t, J = 2.9 Hz), 33.7, 32.7 (t, J = 23.2 Hz), 31.5, 14.0, 4.5. C-5 is a new compound.

[0063] Example 10

[0064]

[0065] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 122.0 mg (0.6 mmol) of compound A-6 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 15 min, compound C-6 was obtained with a yield of 83% (dr = 2.2:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ6.86(d,J=8.8Hz,2H),6.54(d,J=8.4Hz,2H),4.35(q,J=7.2Hz,2H),3.76(s,3H),3.49–3.34(m,3H),3.31(q,J=4.8Hz,1H) ,3.27–3.23(m,1H),3.13(t,J=10.2Hz,1H),2.86–2.78(m,1H),2.72–2. 63(m,1H),2.40–2.26(m,1H),2.24–2.09(m,1H),1.37(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-104.08 (ddd, J = 260.9Hz, 21.8Hz, 11.3Hz, 1F), -106.11 (ddd, J = 260.9Hz, 21.1Hz, 14.3Hz, 1F). 13C NMR (101 MHz, CDCl3) δ 163.9 (t, J = 32.7 Hz), 142.0, 115.7 (t, J = 252.7 Hz), 115.0, 112.4, 110.0, 63.2, 55.9, 53.8, 52.1, 44.8, 35.7 (t, J = 2.9 Hz), 32.8 (t, J = 23.2 Hz), 14.0, 4.7. C-6 is a new compound.

[0066] Embodiment 11

[0067]

[0068] Into a 25 mL quartz reaction tube replaced with argon five times, 114.7 mg (0.6 mmol) of compound A-7 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-7 was obtained with a yield of 75% (dr = 2.3:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ6.95(t,J=8.8Hz,2H),6.47–6.44(m,2H),4.35(q,J=7.2Hz,2H),3.48–3.29(m,4H),3.24(dd,J=8.8Hz,8.0H z,1H),3.11(t,J=10.2Hz,1H),2.87–2.79(m,1H),2.72–2.63(m,1H),2.41–2.27(m,1H),2.23–2.08(m,1H),1.38(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-104.07 (ddd, J=261.9Hz, 22.9Hz, 12.0Hz, 1F), -106.13 (ddd, J=261.9Hz, 22.9Hz, 14.7Hz, 1F), -129.73–-129.80 (m, 1F). 13 C NMR (101 MHz, CDCl3) δ 163.8 (t, J = 32.6 Hz), 155.3 (d, J = 235.6 Hz), 143.9 (d, J = 1.5 Hz), 115.7 (t, J = 252.9 Hz), 115.6 (d, J = 22.2 Hz), 112.2 (d, J = 7.4 Hz), 63.3, 53.7, 52.0, 44.8, 35.7 (t, J = 2.9 Hz), 32.7 (t, J = 23.2 Hz), 14.0, 4.4. C-7 is a new compound.

[0069] Example 12

[0070]

[0071] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 124.6 mg (0.6 mmol) of compound A-8 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 15 min, compound C-8 was obtained with a yield of 90% (dr = 2.1:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ7.19–7.15(m,2H),6.48–6.44(m,2H),4.36(q,J=7.2Hz,2 H),3.49–3.40(m,2H),3.36(dd,J=9.6Hz,3.6Hz,1H),3.30(dd,J=10.0Hz,4.8Hz ,1H),3.24(dd,J=9.6Hz,7.6Hz,1H),3.08(t,J=10.2Hz,1H),2.86–2.79(m,1H), 2.73–2.64(m,1H),2.41–2.27(m,1H),2.22–2.08(m,1H),1.38(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-104.11 (ddd, J=261.5Hz, 22.6Hz, 11.7Hz, 1F), -106.22 (ddd, J=261.5Hz, 21.8Hz, 14.3Hz, 1F). 13 C NMR (101 MHz, CDCl3) δ 163.8 (t, J = 32.6 Hz), 145.7, 128.9, 121.0, 115.6 (t, J = 252.8 Hz), 112.6, 63.3, 53.3, 51.5, 44.7, 35.6 (t, J = 3.0 Hz), 32.6 (t, J = 23.2 Hz), 13.9, 4.3. C-8 is a new compound.

[0072] Example 13

[0073]

[0074] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 151.3 mg (0.6 mmol) of compound A-9 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-9 was obtained with a yield of 84% (dr = 2.0: 1). The ratio of trans: cis is in brackets. Trans: 1H NMR (400MHz, CDCl3) δ7.32–7.28(m,2H),6.44–6.40(m,2H),4.35(q,J=7.2Hz ,2H),3.48–3.40(m,2H),3.36(dd,J=9.6Hz,3.6Hz,1H),3.31(dd,J=9.6Hz,4 .8Hz,1H),3.26–3.22(m,1H),3.08(t,J=10.2Hz,1H),2.87–2.79(m,1H),2.7 3–2.64(m,1H),2.40–2.27(m,1H),2.22–2.08(m,1H),1.37(t,J=7.2Hz,3H). 19 FNMR (376MHz, CDCl3) δ-104.13 (dm, J=260.7Hz, 1F), -106.23 (dm, J=260.7Hz, 1F). 13 C NMR (101 MHz, CDCl3) δ 163.8 (t, J = 26.0 Hz), 146.1, 131.8, 115.6 (t, J = 202.0 Hz), 113.1, 108.1, 63.3, 53.2, 51.4, 44.7, 35.6 (t, J = 2.3 Hz), 32.7 (t, J = 18.6 Hz), 14.0, 4.2. C-9 is a new compound.

[0075] Embodiment 14

[0076]

[0077] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 179.5 mg (0.6 mmol) of compound A-10 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 15 min, compound C-10 was obtained with a yield of 78% (dr = 1.9:1). The ratio of trans: cis is in brackets. Trans: 1H NMR (400MHz, CDCl3) δ7.49–7.45(m,2H),6.36–6.32(m,2H),4.35(q,J=7.2Hz,2 H),3.48–3.40(m,2H),3.36(dd,J=9.6Hz,3.6Hz,1H),3.30(dd,J=10.0Hz,4.8Hz ,1H),3.24(dd,J=9.6Hz,7.6Hz,1H),3.08(t,J=10.2Hz,1H),2.87–2.79(m,1H), 2.73–2.64(m,1H),2.40–2.26(m,1H),2.22–2.05(m,1H),1.37(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-104.60 (ddd, J=261.9Hz, 22.2Hz, 10.9Hz, 1F), -106.67 (ddd,J=261.9Hz, 21.4Hz, 13.9Hz, 1F). 13 C NMR (101 MHz, CDCl3) δ 163.7 (t, J = 32.6 Hz), 146.6, 137.6, 115.6 (t, J = 252.8 Hz), 113.9, 77.0, 63.2, 53.0, 51.3, 44.6, 35.6 (t, J = 3.0 Hz), 32.6 (t, J = 23.3 Hz), 13.9, 4.2. C-10 is a new compound.

[0078] Embodiment 15

[0079]

[0080] 82.9 mg (0.6 mmol) potassium carbonate was weighed into a 25 mL quartz reaction tube, and 119.0 mg (0.6 mmol) of compound A-11 and 75.0 mg (0.3 mmol) of compound B-1 were injected after argon replacement 5 times. After irradiation with 470-475 nm blue light for 10 min, compound C-11 was obtained with a yield of 80% (dr = 1.5:1). The ratio of trans: cis is in brackets. A mixture of diastereomers: 1H NMR(400MHz,CDCl3)δ7.46(d,J=8.8Hz,2H,trans),7.46(d,J=9.2Hz,2H,cis),6.51(d,J=8.8Hz,2H,overlapped),4.35(q,J=7.2Hz,2H,trans),4.36(q,J=7.2Hz,2H,cis),3.81(t,J=8.8Hz,1H,cis),3.62(dd,J=10.0Hz,7.6Hz,1H,cis),3.56–3.48(m,2H,trans),3.44(dd,J=10.0Hz,3.6Hz,1H,overlapped),3.33–3.28(m,2H,trans),3.22–3.13(m,3H,cis),3.05(t,J=10.2Hz,1H,trans),2.90–2.82(m,1H,trans),2.77–2.68(m,1H,trans),2.50–2.27(m,1H,trans),2.50–2.27(m,2H,cis),2.22–2.03(m,1H,trans),2.22–2.03(m,2H,cis),1.37(t,J=7.2Hz,3H,trans),1.38(t,J=7.2Hz,3H,cis). 19 F NMR(376MHz,CDCl3)δ-98.90(ddd,J=262.6Hz,22.6Hz,9.0Hz,1F,cis),-99.87(ddd,J=262.1Hz,22.9Hz,10.5Hz,1F,trans),-102.18(ddd,J=262.1Hz,22.2Hz,14.3Hz,1F,trans),-102.31(ddd,J=262.6Hz,22.2Hz,16.9Hz,1F,cis). 13C NMR(101MHz, CDCl3)δ163.6(t,J=32.4Hz,trans),163.6(t,J=32.5Hz,cis),149.5(trans),149.1(cis),133.5(trans),133.4(cis),12 0.6(cis),120.5(trans),115.5(t,J=253.0Hz,trans),115.3(t,J=252.6Hz,cis),111.5(trans),111.4(cis),97.7(trans),97.6(cis) ,63.3(overlapped),53.6(cis),53.5(cis),52.9(trans),51.0(trans),45.2(cis),44.4(trans),37.9(dd,J=3.2Hz,2.0Hz,cis),36. 3(t,J=23.6Hz,cis),35.4(t,J=2.8Hz,trans),32.5(t,J=23.3Hz,trans),13.9(trans),13.8(cis),5.5(cis),3.7(trans).C-11 is a new compound.

[0081] Example 16

[0082]

[0083] 82.9 mg (0.6 mmol) potassium carbonate was weighed into a 25 mL quartz reaction tube, and 144.8 mg (0.6 mmol) of compound A-12 and 75.0 mg (0.3 mmol) of compound B-1 were injected after argon replacement 5 times. After irradiation with 470-475 nm blue light for 10 min, compound C-12 was obtained with a yield of 89% (dr = 1.8: 1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ7.46 (d, J = 8.4Hz, 2H), 6.55 (d, J = 8.4Hz, 2H), 4.36 (q, J = 7.2Hz, 2H), 3.56–3.48 (m, 2H), 3.44 (dd, J = 10.0Hz, 3.6Hz, 1H), 3.34–3.28(m,2H),3.08(t,J=10.2Hz,1H),2.90–2.82(m,1H),2.76–2. 67(m,1H),2.42–2.28(m,1H),2.23–2.09(m,1H),1.38(t,J=7.2Hz,3H). 19F NMR (376MHz, CDCl3) δ-60.85 (s, 3F), -104.08 (ddd, J = 262.4Hz, 23.3Hz, 12.0Hz, 1F), -106.19 (ddd, J = 262.4Hz, 22.9Hz, 14.3Hz, 1F). 13 C NMR (101 MHz, CDCl3) δ 163.8 (t, J = 32.6 Hz), 149.2, 126.5 (dd, J = 7.6 Hz, 3.9 Hz), 123.7, 117.8 (d, J = 32.5 Hz), 115.6 (t, J = 252.9 Hz), 110.9, 63.3, 53.0, 51.2, 44.6, 35.6, 32.6 (t, J = 23.4 Hz), 14.0, 3.9. C-12 is a new compound.

[0084] Embodiment 17

[0085]

[0086] 82.9 mg (0.6 mmol) potassium carbonate was weighed into a 25 mL quartz reaction tube, and 157.9 mg (0.6 mmol) of compound A-14 and 75.0 mg (0.3 mmol) of compound B-1 were injected after argon replacement 5 times. After irradiation with 470-475 nm blue light for 10 min, compound C-13 was obtained with a yield of 74% (dr = 3.0: 1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ4.35(q,J=7.2Hz,2H),3.82–3.77(m,1H),3.62–3.57(m,1H),3.56–3.48(m,2H),3.28(q,J=4.8Hz,1H) ,3.14(t,J=10.2Hz,1H),2.80–2.72(m,1H),2.67–2.58(m,1H),2.38–2.24(m,1H),2.22–2.08(m,1H),1.38(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-104.26 (ddd, J=261.7Hz, 21.8Hz, 11.3Hz, 1F), -106.05 (ddd, J=261.7Hz, 21.4Hz, 13.9Hz, 1F), -154.56 (d, J=20.3Hz, 2F), -164.27 (dd, J=22.2Hz, 18.8Hz, 2F), -169.42–-169.59 (m, 1F). 13C NMR (101 MHz, CDCl3) δ163.7 (t, J = 32.7 Hz), 139.9 (dm, J = 244.9 Hz), 138.2 (dm, J = 248.4 Hz), 134.0 (dm, J = 250.2 Hz), 123.6–123.3 (m), 115.6 (t, J = 252.8 Hz), 63.2, 56.2 (t, J = 5.2 Hz), 54.5 (t, J = 5.3 Hz), 44.8, 35.7, 32.3 (t, J = 23.3 Hz), 13.8, 3.3. C-13 is a new compound.

[0087] Embodiment 18

[0088]

[0089] 82.9 mg (0.6 mmol) potassium carbonate was weighed into a 25 mL quartz reaction tube, and 147.2 mg (0.6 mmol) of compound A-15 and 75.0 mg (0.3 mmol) of compound B-1 were injected after argon replacement 5 times. After irradiation with 470-475 nm blue light for 10 min, compound C-14 was obtained with a yield of 91% (dr = 1.6: 1). The ratio of trans: cis is in brackets. A mixture of diastereomers: 1 H NMR (400MHz, CDCl3) δ7.91 (d, J=6.0Hz, 2H, overlapped), 6.53–6.48 (m, 2H, overlapped), 4.39–4.29 (m, 4H, overlapped), 3.85 –3.78(m,1H,cis),3.67–3.59(m,1H,cis),3.57–3.48(m,2H,trans),3.47–3.41(m,1H,overlapped),3.34–3.24(m,2H,trans) ,3.23–3.13(m,3H,cis),3.10–3.03(m,1H,trans),2.88–2.79(m,1H,trans),2.75–2.64(m,1H,trans),2.48–2.27(m,1H,tran s),2.48–2.27(m,2H,cis),2.21–2.06(m,1H,trans),2.21–2.06(m,2H,cis),1.40–1.35(m,6H,cis),1.40–1.30(m,6H,trans). 19F NMR (376MHz, CDCl3) δ-103.13 (ddd, J=262.8Hz, 22.2Hz, 9.4Hz, 1F, cis), -104.11 (ddd, J=262.1Hz, 22.2Hz, 11.3Hz, 1 F, trans), -106.28 (ddd, J=262.8Hz, 21.4Hz, 16.2Hz, 1F, cis), -106.13 (ddd, J=261.7Hz, 21.4Hz, 13.5Hz, 1F, trans). 13 C NMR (101MHz, CDCl3) δ166.9(cis),166.8(trans),163.7(t,J=30.7Hz,trans),163.6(t,J=32.3Hz,cis),150.2(trans),149.9(cis),131.3(ov erlapped),117.8(cis),117.7(trans),115.6(t,J=252.8Hz,trans),115.4(t,J=252.6Hz,cis),110.7(trans),110.6(cis),63.3(overlapped ),60.2(overlapped),53.8(cis),53.7(trans),53.0(trans),51.2(trans),45.5(cis),44.6(trans),38.0(t,J=2.7Hz,cis),36.6(t,J=23.7H z, cis), 35.5 (t, J = 2.7 Hz, trans), 32.6 (t, J = 23.3 Hz, trans), 14.4 (overlapped), 14.0 (cis), 13.9 (trans), 5.8 (cis), 3.8 (trans). C-14 is a new compound.

[0090] Embodiment 19

[0091]

[0092] Into a 25 mL quartz reaction tube replaced with argon five times, 105.1 mg (0.6 mmol) of compound A-16 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 15 min, compound C-15 was obtained with a yield of 62% (dr = 2.1:1). The ratio of trans: cis is in brackets. A mixture of diastereomers: 1H NMR(400MHz,CDCl3)δ8.32(d,J=4.8Hz,2H,overlapped),6.53–6.50(m,1H,overlapped),4.34(q,J=7.2Hz,2H,overlapped),4.15(dd,J=12.0Hz,8.0Hz,1H,cis),3.96(dd,J=11.6Hz,7.6Hz,1H,cis),3.78(dd,J=11.2Hz,7.2Hz,1H,trans),3.73(d,J=5.2Hz,2H,trans),3.50(dd,J=11.2Hz,7.6Hz,1H,trans),3.42(dd,J=10.0Hz,3.6Hz,1H,cis),3.37–3.34(m,1H,cis),3.30(dd,J=10.0Hz,4.8Hz,1H,overlapped),3.20–3.15(m,1H,cis),3.08(t,J=10.2Hz,1H,trans),2.86–2.79(m,1H,trans),2.72–2.64(m,1H,trans),2.47–2.25(m,1H,trans),2.47–2.25(m,2H,cis),2.21–2.03(m,1H,trans),2.21–2.03(m,2H,cis),1.36(t,J=7.2Hz,3H,overlapped). 19 F NMR(376MHz,CDCl3)δ-103.08(ddd,J=263.2Hz,21.8Hz,10.8Hz,1F,cis),-104.23(ddd,J=261.7Hz,21.8Hz,12.0Hz,1F,trans),-105.93(ddd,J=261.7Hz,21.1Hz,13.9Hz,1F,trans),-106.08(ddd,J=263.2Hz,21.1Hz,16.2Hz,1F,cis). 13C NMR(101MHz, CDCl3)δ163.8(t,J=32.4Hz,trans),163.7(t,J=32.4Hz,cis),160.1(trans),159.7(cis),157.7(overlap ped),115.6(t,J=252.7Hz,trans),115.4(t,J=252.7Hz,cis),109.7(trans),109.6(cis),63.2(trans),63.1(cis),52 .6(cis),52.5(cis),51.9(trans),50.1(trans),45.5(cis),44.5(trans),38.0(t,J=3.0Hz,cis),36.6(t,J=23.5Hz,cis),35.5(t,J=3.0Hz,trans),32.4(t,J=23.4Hz,trans),14.0(cis),13.9(trans),5.7(cis),3.6(trans).C-15 is a new compound.

[0093] Embodiment 20

[0094]

[0095] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 134.6 mg (0.6 mmol) of compound A-17 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 15 min, compound C-16 was obtained with a yield of 81% (dr = 1.6:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ7.89(d,J=8.8Hz,1H),7.76(d,J=8.4Hz,1H),7.60(d,J=7.6Hz,1H),7.56–7.52(t ,J=7.2Hz,1H),7.21(t,J=7.4Hz,1H),6.72(d,J=8.8Hz,1H),4.36(q,J=7.2Hz,2H),3.86–3.78(m,2H), 3.75–3.71(m,1H),3.57(dd,J=10.8Hz,7.6Hz,1H),3.32(dd,J=10.0Hz,5.2Hz,1H),3.12(t,J=10.2Hz, 1H),2.90–2.82(m,1H),2.76–2.67(m,1H),2.41–2.26(m,1H),2.24–2.11(m,1H),1.37(t,J=7.2Hz,3H).19 F NMR (376MHz, CDCl3) δ-104.47 (br.d, J=260.8Hz, 1F), -105.95 (br.d, J=260.8Hz, 1F). 13 C NMR (101 MHz, CDCl3) δ 163.8 (t, J = 32.6 Hz), 155.1, 147.7, 137.6, 129.7, 127.4, 125.9, 122.7, 122.0, 115.7 (t, J = 252.8 Hz), 109.7, 63.3, 52.3, 50.5, 44.5, 35.6 (t, J = 2.5 Hz), 32.4 (t, J = 23.3 Hz), 13.9, 3.9. C-16 is a new compound.

[0096] Embodiment 21

[0097]

[0098] Into a 25 mL quartz reaction tube replaced with argon five times, 104.5 mg (0.6 mmol) of compound A-18 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 15 min, compound C-17 was obtained with a yield of 80% (dr = 1.9:1). The ratio of trans: cis is in brackets. A mixture of diastereomers: 1H NMR(400MHz,CDCl3)δ8.14(dd,J=4.8Hz,1.6Hz,1H,overlapped),7.47–7.42(m,1H,overlapped),6.57–6.54(m,1H,overlapped),6.35(d,J=8.4Hz,1H,overlapped),4.34(q,J=7.2Hz,2H,cis),4.33(q,J=7.2Hz,2H,trans),3.97–3.93(m,1H,cis),3.83–3.78(m,1H,cis),3.66–3.61(m,2H,trans),3.57(dd,J=10.8Hz,4.4Hz,1H,trans),3.43–3.36(m,1H,overlapped),3.31–3.15(m,1H,trans),3.31–3.15(m,3H,cis),3.08(t,J=10.0Hz,1H,trans),2.85–2.78(m,1H,trans),2.71–2.62(m,1H,trans),2.46–2.24(m,1H,trans),2.46–2.24(m,2H,cis),2.21–2.02(m,1H,trans),2.21–2.02(m,2H,cis),1.36(t,J=7.2Hz,3H,cis),1.35(t,J=7.2Hz,3H,trans). 19 F NMR(376MHz,CDCl3)δ-103.02(ddd,J=262.2Hz,21.4Hz,9.8Hz,1F,cis),-104.13(ddd,J=261.5Hz,21.1Hz,10.9Hz,1F,trans),-105.98(ddd,J=261.5Hz,21.4Hz,13.9Hz,1F,trans),-106.17(ddd,J=262.2Hz,20.7Hz,15.4Hz,1F,cis). 13C NMR(101MHz, CDCl3)δ163.8(t,J=32.6Hz,trans),163.7(t,J=32.6Hz,cis),156.7(trans),156.5(cis),147.9(cis),147.8(trans),13 7.2(trans),137.1(cis),115.6(t,J=252.8Hz,trans),115.5(t,J=252.5Hz,cis),111.9(overlapped),106.4(trans),106.3(cis),63. 2(trans),63.1(cis),52.8(cis),52.7(cis),52.1(trans),50.3(trans),45.5(cis),44.5(trans),38.0(dd,J=3.2Hz,2.4Hz,cis),36. 7(t,J=23.5Hz,cis),35.6(t,J=3.0Hz,trans),32.4(t,J=23.3Hz,trans),14.0(cis),13.9(trans),6.2(cis),4.0(trans).C-17 is a new compound.

[0099] Embodiment 22

[0100]

[0101] 82.9 mg (0.6 mmol) potassium carbonate was weighed into a 25 mL quartz reaction tube, and 115.3 mg (0.6 mmol) of compound A-19 and 75.0 mg (0.3 mmol) of compound B-1 were injected after argon replacement 5 times. After irradiation with 470-475 nm blue light for 10 min, compound C-18 was obtained with a yield of 48% (dr = 1.7:1). The ratio of trans: cis is in brackets. A mixture of diastereomers: 1H NMR(400MHz,CDCl3)δ7.91–7.89(m,1H,overlapped),7.18–7.12(m,1H,overlapped),6.55–6.51(m,1H,overlapped),4.33(q,J=7.2Hz,2H,overlapped),4.11–4.06(m,1H,cis),3.93–3.89(m,1H,cis),3.81–3.69(m,3H,trans),3.61–3.56(m,1H,trans),3.47–3.38(m,3H,cis),3.28(dd,J=10.0Hz,5.2Hz,1H,trans),3.19–3.14(m,1H,cis),3.10(t,J=10.2Hz,1H,trans),2.79–2.71(m,1H,trans),2.65–2.56(m,1H,trans),2.44–2.02(m,2H,trans),2.44–2.02(m,4H,cis),1.36(t,J=7.2Hz,3H,cis),1.35(t,J=7.2Hz,3H,trans). 19 FNMR(376MHz,CDCl3)δ-101.28(dm,J=261.7Hz,1F,cis),-102.21(dm,J=260.9Hz,1F,trans),-103.62(dm,J=260.9Hz,1F,overlapped),-133.17(s,1F,cis),-133.45(s,1F,trans). 13CNMR(101MHz,CDCl3)δ163.8(t,J=32.7Hz,trans),163.7(t,J=32.7Hz,cis),147.6(d,J=2 54.5Hz,cis),147.5(d,J=254.2Hz,trans),147.4(d,J=8.6Hz,trans),147.2(d,J=8.5Hz, cis),142.7(d,J=5.2Hz,cis),142.6(d,J=5.3Hz,trans),122.3(d,J=18.1Hz,overlapped ),115.6(t,J=252.7Hz,trans),115.4(t,J=252.6Hz,cis),112.5(d,J=1.8Hz,cis),112.4( d,J=1.6Hz,trans),63.2(overlapped),54.3(d,J=5.7Hz,cis),54.1(d,J=4.9Hz,cis),53 .4(d,J=5.0Hz,trans),51.7(d,J=5.8Hz,trans),45.0(d,J=2.2Hz,cis),44.1(d,J=1.8Hz ,trans),37.7(q,J=2.6Hz,cis),36.6(t,J=23.6Hz,cis),35.2(dd,J=5.3Hz,2.7Hz,trans ), 32.4 (t, J = 23.3Hz, trans), 13.9 (cis), 13.8 (trans), 6.2 (cis), 3.8 (trans). C-18 is a new compound.

[0102] Embodiment 23

[0103]

[0104] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 104.0 mg (0.6 mmol) of compound A-1 and 103.8 mg (0.3 mmol) of compound B-2 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-19 was obtained with a yield of 83% (dr = 3.0: 1). The ratio of trans: cis is in brackets. Trans: 1H NMR (400MHz, CDCl3) δ7.29–7.25(m,2H),6.76(t,J=7.2Hz,1H),6.61(d,J=8.0Hz,2H),3.56–3.50(m,2H),3.45(dd,J=9 .6Hz, 3.6Hz, 1H), 3.34–3.26 (m, 2H), 3.13 (t, J = 10.0Hz, 1H), 2.92–2.80 (m, 2H), 2.43–2.28 (m, 1H), 2.25–2.10 (m, 1H). 19 F NMR(376MHz, CDCl3)δ-81.02(t,J=10.0Hz,3F),-112.73(dm,J=267.0Hz,1F),-1 14.63(dm,J=263.2Hz,1F),-124.22–-124.30(m,2F),-125.85–-125.95(m,2F). 13 C NMR (101 MHz, CDCl3) δ147.0, 129.3, 120.0–100.0 (m), 116.7, 111.8, 53.3, 51.7 (d, J=3.4 Hz), 44.7, 34.7, 29.0 (t, J=21.7 Hz), 3.7. C-19 is a new compound.

[0105] Embodiment 24

[0106]

[0107] Into a 25 mL quartz reaction tube replaced with argon five times, 114.7 mg (0.6 mmol) of compound A-7 and 103.8 mg (0.3 mmol) of compound B-2 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-20 was obtained with a yield of 72% (dr = 3.2: 1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ6.97(t,J=8.8Hz,2H),6.51(dd,J=9.2Hz,4.4Hz,2H),3.53–3.45(m,2H),3.40(dd,J=9.6Hz ,3.6Hz,1H),3.31–3.26(m,2H),3.13(t,J=9.8Hz,1H),2.92–2.80(m,2H),2.43–2.28(m,1H),2.25–2.10(m,1H). 19F NMR(376MHz, CDCl3)δ-81.01–-81.07(m,3F),-112.71(dm,J=269.6Hz,1F),-114.68(dm ,J=277.1Hz,1F),-124.27(d,J=4.9Hz,2F),-125.86–-125.96(m,2F),-129.16(s,1F). 13 C NMR (101 MHz, CDCl3) δ146.6, 137.7, 129.2, 120.0–100.0 (m), 113.9, 53.1, 51.4 (d, J=3.4 Hz), 44.6, 34.7, 29.0 (t, J=21.9 Hz), 3.5. C-20 is a new compound.

[0108] Embodiment 25

[0109]

[0110] Inject 124.6 mg (0.6 mmol) of compound A-8 and 103.8 mg (0.3 mmol) of compound B-2 into a 25 mL quartz reaction tube after argon replacement 5 times. After irradiation with 470-475 nm blue light for 15 min, compound C-21 was obtained with a yield of 83% (dr = 2.6:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400 MHz, CDCl3) δ7.19 (dm, J = 9.2 Hz, 2H), 6.50 (dm, J = 9.2 Hz, 2H), 3.53–3.46 (m, 2H), 3.40 (dd, J = 9.6 Hz, 3.2 Hz,1H),3.30–3.25(m,2H),3.11(t,J=9.8 Hz,1H),2.92–2.80(m,2H),2.43–2.28(m,1H),2.24–2.09(m,1H). 19 F NMR (376 MHz, CDCl3) δ-81.00–-81.05(m,3F),-112.66(dm,J=274.1 Hz,1F),-114.65(dm,J=274.9 Hz,1F),-124.25(s,2F),-125.90(s,2F). 13 C NMR (101 MHz, CDCl3) δ145.6, 129.1, 121.6, 120.0–100.0 (m), 112.9, 53.5, 51.8 (d, J=3.3 Hz), 44.6, 34.7, 29.0 (t, J=22.2 Hz), 3.5. C-21 is a new compound.

[0111] Embodiment 26

[0112]

[0113] Inject 151.3 mg (0.6 mmol) of compound A-9 and 103.8 mg (0.3 mmol) of compound B-2 into a 25 mL quartz reaction tube after argon replacement 5 times. After irradiation with 470-475 nm blue light for 15 min, compound C-22 was obtained with a yield of 76% (dr = 2.4:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400 MHz, CDCl3) δ7.32 (dm, J = 9.2 Hz, 2H), 6.44 (dm, J = 9.2 Hz, 2H), 3.52–3.45 (m, 2H), 3.40 (dd, J = 9.6 Hz, 3.2 Hz,1H),3.29–3.24(m,2H),3.10(t,J=10.0 Hz,1H),2.92–2.80(m,2H),2.42–2.28(m,1H),2.24–2.08(m,1H). 19 F NMR (376 MHz, CDCl3) δ-81.00–-81.04(m,3F),-112.74(dm,J=272.6 Hz,1F),-114.71(dm,J=274.5 Hz,1F),-124.26(s,2F),-125.92(s,2F). 13 C NMR (101 MHz, CDCl3) δ146.0, 131.9, 120.0–100.0 (m), 113.2, 108.4, 53.2, 51.5 (d, J=3.4 Hz), 44.6, 34.7, 29.0 (t, J=21.9 Hz), 3.6. C-22 is a new compound.

[0114] Embodiment 27

[0115]

[0116] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 179.5 mg (0.6 mmol) of compound A-10 and 103.8 mg (0.3 mmol) of compound B-2 were injected. After irradiation with 470-475 nm blue light for 15 min, compound C-23 was obtained with a yield of 71% (dr = 2.6:1). The ratio of trans: cis is in brackets. Trans: 1H NMR(400MHz, CDCl3) δ7.48(d,J=8.4Hz,2H),6.34(d,J=8.8Hz,2H),3.51–3.45(m,2H),3.39(dd,J=9.6Hz,3.2 Hz,1H),3.28–3.24(m,2H),3.09(t,J=10.0Hz,1H),2.91–2.79(m,2H),2.42–2.28(m,1H),2.23–2.08(m,1H). 19 FNMR(376MHz, CDCl3)δ-80.70(s,3F),-112.35(dm,J=272.2Hz,1F),-114.34(dm,J=272.6Hz,1F),-123.93(s,2F),-125.57(s,2F). 13 C NMR (101 MHz, CDCl3) δ146.6, 137.7, 129.2, 120.0–100.0 (m), 113.9, 53.1, 51.4 (d, J=3.4 Hz), 44.6, 34.7, 29.0 (t, J=21.9 Hz), 3.5. C-23 is a new compound.

[0117] Embodiment 28

[0118]

[0119] 82.9 mg (0.6 mmol) potassium carbonate was weighed into a 25 mL quartz reaction tube, and after argon replacement for 5 times, 162.1 mg (0.6 mmol) of compound A-13 and 103.8 mg (0.3 mmol) of compound B-2 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-24 was obtained with a yield of 88% (dr = 2.0: 1). The ratio of trans: cis is in brackets. Trans: 1 HNMR (400MHz, CDCl3) δ7.31(dd,J=8.8Hz,8.0Hz,1H),6.31(dd,J=11.2Hz,2.4Hz,1H),6.22(dd,J=8.8Hz,2.8Hz,1H),3.52–3.44(m,2H ),3.38(dd,J=9.6Hz,3.2Hz,1H),3.29–3.23(m,2H),3.08(t,J=10.0Hz,1H),2.92–2.81(m,2H),2.43–2.29(m,1H),2.23–2.08(m,1H). 19F NMR (376MHz, CDCl3) δ-81.04(s,3F),-107.06(s,1F),-112.66(dm,J=274.6Hz,1F),-114.66(dm,J=272.6Hz,1F),-124.25(s,2F),-125.91(s,2F). 13 C NMR (101 MHz, CDCl3) δ159.7 (d, J = 244.9 Hz), 147.8 (d, J = 10.1 Hz), 133.3 (d, J = 2.5 Hz), 120.0–100.0 (m), 108.8 (d, J = 2.6 Hz), 99.9 (d, J = 26.7 Hz), 94.3 (d, J = 21.4 Hz), 53.4, 51.6 (d, J = 3.5 Hz), 44.5, 34.7 (t, J = 2.3 Hz), 29.0 (t, J = 22.0 Hz), 3.2. C-24 is a new compound.

[0120] Embodiment 29

[0121]

[0122] 82.9 mg (0.6 mmol) potassium carbonate was weighed into a 25 mL quartz reaction tube, and 147.2 mg (0.6 mmol) of compound A-15 and 103.8 mg (0.3 mmol) of compound B-2 were injected after argon replacement 5 times. After irradiation with 470-475 nm blue light for 10 min, compound C-25 was obtained with a yield of 90% (dr = 1.9: 1). The ratio of trans: cis is in brackets. Trans: 1 HNMR(400MHz, CDCl3) δ7.93(d,J=8.8Hz,2H),6.52(d,J=8.8Hz,2H),4.32(q,J=7.2Hz,2H),3.60–3.55(m,2H),3.49(dd,J=10.0Hz,2.8Hz,1H),3.36– 3.32(m,1H),3.28(dd,J=10.0Hz,4.4Hz,1H),3.08(t,J=10.0Hz,1H),2.93 –2.81(m,2H),2.44–2.29(m,1H),2.24–2.09(m,1H),1.37(t,J=7.0Hz,3H). 19F NMR(376MHz, CDCl3)δ-82.83–-82.96(m,3F),-114.51(dm,J=270.7Hz,1F),-11 6.50(dm,J=270.0Hz,1F),-126.06–-126.16(m,2F),-127.72–-127.83(m,2F). 13 C NMR (101 MHz, CDCl3) δ166.9, 150.2, 131.4, 120.0–100.0 (m), 118.0, 110.8, 60.2, 53.0, 51.3 (d, J=3.5 Hz), 44.5, 34.7, 29.0 (t, J=21.5 Hz), 14.4, 3.1. C-25 is a new compound.

[0123] Embodiment 30

[0124]

[0125] Into a 25 mL quartz reaction tube replaced with argon five times, 155.6 mg (0.6 mmol) of compound A-20 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-26 was obtained with a yield of 89% (dr = 3.3:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ7.30–7.26(m,2H),7.23–7.17(m,3H),4.33(q,J=7.2Hz,2H),4.32(q,J=7.2Hz,2H),3.61(s,3H),3.59(t,J=7.6Hz,1H), 3.26–2.94(m,6H),2.76–2.62(m,3H),2.50–2.43(m,1H),2.30–2.14(m ,1H),2.10–1.95(m,1H),1.36(t,J=7.2Hz,3H),1.35(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-103.94 (ddd, J=259.8Hz, 21.4Hz, 11.3Hz, 1F), -106.24 (dm, J=259.4Hz, 1F). 13CNMR (101 MHz, CDCl3) δ 172.5, 164.0 (t, J = 32.8 Hz), 137.7, 128.9, 128.8, 128.3, 126.5, 115.8 (t, J = 252.7 Hz), 65.7, 65.6, 63.1, 63.0, 56.4, 54.9, 54.7, 53.4, 51.3, 43.8, 43.7, 37.0, 36.9, 35.0, 33.0 (t, J = 23.2 Hz), 32.9 (t, J = 23.1 Hz), 14.0, 6.1. C-26 is a new compound.

[0126] Embodiment 31

[0127]

[0128] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 164.0 mg (0.6 mmol) of compound A-21 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-27 was obtained with a yield of 92% (dr = 2.7:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ7.30–7.26(m,2H),7.22–7.19(m,3H),4.33(q,J=7.2Hz,2H),4.32(q,J= 7.2Hz,2H),4.08(q,J=7.2Hz,2H),3.57(q,J=8.0Hz,1H),3.28–3.14(m,3H),3.11–3.01(m,2H) ,2.99–2.94(m,1H),2.78–2.60(m,3H),2.53–2.41(m,1H),2.31–2.15(m,1H),2.10–1.96(m,1 H),1.37(t,J=7.2Hz,3H),1.36(t,J=7.2Hz,3H),1.15(t,J=7.2Hz,3H),1.14(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-99.78 (ddd, J=259.8Hz, 21.8Hz, 12.0Hz, 1F), -102.07 (dm, J=259.4Hz, 1F). 13CNMR (101 MHz, CDCl3) δ 172.1, 164.0 (t, J = 32.8 Hz), 137.8, 128.9, 128.8, 128.2, 126.4, 115.8 (t, J = 252.5 Hz), 65.7, 65.6, 63.0, 63.0, 60.3, 60.2, 56.3, 54.9, 54.7, 53.3, 43.8, 43.7, 37.1, 37.0, 35.0 (t, J = 2.9 Hz), 33.0 (t, J = 23.0 Hz), 32.8 (t, J = 23.0 Hz), 14.2, 13.9, 6.2. C-27 is a new compound.

[0129] Embodiment 32

[0130]

[0131] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 180.9 mg (0.6 mmol) of compound A-22 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-28 was obtained with a yield of 93% (dr = 2.4:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ7.28–7.24(m,2H),7.21–7.17(m,3H),4.33(q,J=7.2H z,2H),4.32(q,J=7.2Hz,2H),3.46(dd,J=16.0Hz,8.4Hz,1H),3.28–2.90(m, 6H),2.79–2.59(m,3H),2.52–2.39(m,1H),2.30–2.14(m,1H),2.10–1.96(m, 1H),1.36(t,J=7.2Hz,3H),1.35(t,J=7.2Hz,3H),1.34(s,9H),1.33(s,9H). 19 F NMR (376MHz, CDCl3) δ-99.78 (dm, J=259.1Hz, 1F), -102.04 (dm, J=259.1Hz, 1F). 13C NMR (101 MHz, CDCl3) δ 171.4, 171.3, 164.0 (t, J = 32.8 Hz), 138.0, 129.1, 129.0, 128.1, 126.3, 115.9 (t, J = 252.4 Hz), 81.1, 81.0, 66.2, 66.0, 63.1, 63.0, 56.3, 54.8, 54.6, 53.1, 44.0, 43.9, 37.1, 35.1 (t, J = 2.7 Hz), 35.0 (t, J = 2.9 Hz), 33.1 (t, J = 22.9 Hz), 32.9 (t, J = 22.9 Hz), 28.0, 13.9, 6.3, 6.2. C-28 is a new compound.

[0132] Embodiment 33

[0133]

[0134] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 182.6 mg (0.6 mmol) of compound A-23 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-29 was obtained with a yield of 62% (dr = 2.8:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ8.14 (d, J=8.4Hz, 2H), 7.37 (dd, J=8.4Hz, 5.6Hz, 2H), 4.3 2(q,J=7.2Hz),4.31(q,J=7.2Hz),3.69–3.63(m,1H),3.66(s,3H),3.65(s,3H), 3.20–3.12(m,3H),3.10–2.98(m,3H),2.76–2.59(m,3H),2.53–2.43(m,1H),2.2 8–2.12(m,1H),2.06–1.92(m,1H),1.35(t,J=7.2Hz,3H),1.34(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-103.92 (dm, J = 259.8Hz, 1F), -106.52 (dm, J = 260.2Hz, 1F). 13C NMR (101 MHz, CDCl3) δ 171.8, 163.9 (t, J = 32.8 Hz), 146.7, 145.8, 129.8, 129.7, 123.6, 123.5, 115.7 (t, J = 252.7 Hz), 64.4, 63.2, 63.1, 56.1, 54.4, 54.2, 52.8, 51.6, 44.0, 43.9, 36.6, 36.4, 35.1 (t, J = 2.3 Hz), 35.0 (t, J = 2.6 Hz), 32.9 (t, J = 23.0 Hz), 32.8 (t, J = 23.0 Hz), 13.9, 5.7. C-29 is a new compound.

[0135] Embodiment 34

[0136]

[0137] Into a 25 mL quartz reaction tube replaced with argon five times, 176.3 mg (0.6 mmol) of compound A-24 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 15 min, compound C-30 was obtained with a yield of 94% (dr = 2.7:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ7.24 (d, J=8.4Hz, 2H), 7.12 (dd, J=8.4Hz, 4.4Hz, 2H), 4.33 (q, J=7.2Hz ,2H),4.32(q,J=7.2Hz,2H),3.63(s,3H),3.62(s,3H),3.55(q,J=7.6Hz,1H),3.21–3.17(m, 1H),3.14–3.10(m,1H),3.07–2.98(m,3H),2.94–2.88(m,1H),2.75–2.59(m,3H),2.52–2.40 (m,1H),2.29–2.13(m,1H),2.08–1.94(m,1H),1.36(t,J=7.2Hz,3H),1.35(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-103.95 (dm, J=259.8Hz, 1F), -106.33 (dm, J=259.8Hz, 1F). 13C NMR (101 MHz, CDCl3) δ 172.2, 163.9 (t, J = 32.8 Hz), 163.3, 132.2, 130.3, 103.2, 128.4, 128.4, 115.8 (t, J = 252.5 Hz), 65.3, 65.2, 63.1, 63.1, 56.2, 54.7, 54.6), 53.2, 51.4, 43.8, 43.8, 36.3, 36.2, 35.0 (t, J = 2.8 Hz), 34.9 (t, J = 2.7 Hz), 33.0 (t, J = 23.0 Hz), 32.8 (t, J = 23.1 Hz), 13.9, 6.0. C-30 is a new compound.

[0138] Embodiment 35

[0139]

[0140] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 204.3 mg (0.6 mmol) of compound A-25 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-31 was obtained with a yield of 86% (dr = 3.4:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ4.56 (drs, 1H), 4.31 (q, J = 7.2Hz, 2H), 3.68 (s, 3H), 3 .28–3.17(m,3H),3.13–2.96(m,4H),2.71–2.60(m,2H),2.58–2.53(m,1H), 2.50–2.41(m,1H),2.31–2.15(m,1H),2.13–1.97(m,1H),1.77–1.57(m,2H) ,1.51–1.38(m,2H),1.42(s,9H),1.34(t,J=7.2Hz,3H),1.38–1.18(m,2H). 19 FNMR (376MHz, CDCl3) δ-99.65 (dm, J=261.7Hz, 1F), -102.01 (dm, J=260.2Hz, 1F). 13CNMR(101MHz, CDCl3)δ173.3,173.2,163.9(t,J=32.8Hz),163.9(t,J=32.8Hz),1 55.8,115.8(t,J=252.5Hz),115.8(t,J=252.5Hz),78.9,63.7,63.6,63.0,56.1,5 4.8,54.5,53.2,51.2,43.7,43.5,40.2,34.9 (t, J = 3.0 Hz),33.0 (t, J = 23.1 Hz),32.8 (t, J = 23.1 Hz),30.5,30.4,29.6,28.3,23.3,23.2,13.9,6.3,6.1. C-31 is a new compound.

[0141] Embodiment 36

[0142]

[0143] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 119.6 mg (0.6 mmol) of compound A-26 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-32 was obtained with a yield of 89% (dr = 1.0: 1). The ratio of trans: cis is in brackets. Trans: 1 H NMR(400MHz, CDCl3)δ4.33(q,J=7.2Hz,2H),3.90–3.85(m,1H),3.73(s,3H),3.72–3.66(m,1H),3.61–3.57(m,1H),3.29–3.24(m,1H),3.23–3.15 (m,2H),3.13–3.07(m,1H),2.84–2.78(m,2H),2.76–2.66(m,1H),2.61–2 .51(m,2H),2.35–2.19(m,1H),2.17–2.02(m,1H),1.36(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-99.73 (ddd, J=260.2Hz, 21.8Hz, 11.7Hz, 1F), -99.90 (ddd, J=260.6Hz, 21.8Hz, 11.7Hz, 1F), -101.95 (dm, J=260.2Hz, 1F). 13C NMR (101 MHz, CDCl3) δ 171.0, 170.9, 163.9 (t, J = 32.8 Hz), 163.9 (t, J = 32.7 Hz), 115.8 (t, J = 252.3 Hz), 115.7 (t, J = 252.7 Hz), 64.7, 63.2, 60.6, 60.5, 56.0, 55.1, 54.3, 53.4, 51.7, 51.7, 44.0, 43.8, 35.2 (t, J = 2.9 Hz), 35.2 (t, J = 2.8 Hz), 32.9 (t, J = 23.2 Hz), 32.6 (t, J = 23.0 Hz), 13.9, 5.7, 5.4. C-32 is a new compound.

[0144] Embodiment 37

[0145]

[0146] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 173.6 mg (0.6 mmol) of compound A-27 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-33 was obtained with a yield of 78% (dr = 5.4:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ7.36–7.25(m,5H),4.56–4.50(m,2H),4.30(q,J=7.2Hz,2H),3.75–3.68(m,2H),3.71(s,3H),3.58–3.54(m,1H),3 .26–3.05(m,4H),2.72–2.62(m,2H),2.61–2.57(m,1H),2.52–2.42(m,1H),2.32–2.16(m,1H),2.13–1.98(m,1H),1.34(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-99.68 (ddd, J=259.8Hz, 21.4Hz, 12.0Hz, 1F), -101.96 (dm, J=259.8Hz, 1F). 13C NMR (101MHz, CDCl3) δ171.4,171.4,163.9(t,J=32.8Hz),163.9(t,J=32.8Hz),137.7,1 28.3,127.6,127.6,127.6,115.8(t,J=252.6Hz),115.8(t,J=252.6Hz),73.3,73.2,69 .3,69.3,64.2,64.1,63.0,56.9,56.2,55.1,54.4,51.6,43.6,43.5,35.0(t,J=2.7Hz),34.9(t,J=2.8Hz),33.0(t,J=22.9Hz),32.7(t,J=22.8Hz),13.9,6.3,6.2.C-33 is a new compound.

[0147] Embodiment 38

[0148]

[0149] Into a 25 mL quartz reaction tube that had been replaced with argon five times, 128.0 mg (0.6 mmol) of compound A-28 and 75.0 mg (0.3 mmol) of compound B-1 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-34 was obtained with a yield of 86% (dr = 2.4:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ7.35–7.31(m,1H),7.25–7.16(m,3H),4.31(q,J=6.8Hz,2 H),4.33–4.21(m,1H),3.26–3.22(m,1H),3.14–3.05(m,2H),3.04–2.96(m,2H), 2.85–2.78(m,1H),2.73–2.62(m,1H),2.58–2.52(m,1H),2.49–2.41(m,2H),2.3 4–2.24(m,1H),2.22–2.01(m,3H),1.34(t,J=7.2Hz,3H),1.34(t,J=7.2Hz,3H). 19 F NMR (376MHz, CDCl3) δ-99.88 (dm, J=259.4Hz, 1F), -101.80 (dm, J=264.3Hz, 1F). 13C NMR (101 MHz, CDCl3) δ 164.0 (t, J = 33.0 Hz), 143.9, 142.9, 127.4, 126.0, 126.0, 125.2, 125.2, 124.7, 115.9 (t, J = 252.4 Hz), 66.2, 66.2, 63.0, 56.6, 56.2, 54.8, 54.5, 43.4, 43.3, 34.8 (t, J = 2.8 Hz), 34.8 (t, J = 2.9 Hz), 33.2 (t, J = 23.0 Hz), 30.6, 30.6, 27.3, 27.3, 13.9, 6.8, 6.7. C-34 is a new compound.

[0150] Embodiment 39

[0151]

[0152] Into a 25 mL quartz reaction tube replaced with argon five times, 204.3 mg (0.6 mmol) of compound A-25 and 103.8 mg (0.3 mmol) of compound B-2 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-35 was obtained with a yield of 58% (dr = 3.4:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR(400MHz, CDCl3)δ4.55(drs,1H),3.70(s,3H),3.32–3.28(m,1H),3.24–3.02(m,6H),2.77–2.60(m,4H), 2.31–2.19(m,1H),2.16–2.01(m,1H),1.80–1.62(m,2H),1.53–1.47(m,2H),1.42(s,9H),1.39–1.24(m,2H). 19 F NMR(376MHz, CDCl3)δ-81.05–-81.10(m,3F),-112.78(dm,J=264.3Hz,1F),-114.93(dm,J=264.7Hz,1F),-124.46(s,2F),-125.93–-126.00(m,2F). 13C NMR (101 MHz, CDCl3) δ173.3, 173.3, 155.9, 120.0–100.0 (m), 79.1, 63.6, 63.5, 56.1, 54.6, 54.5 (d, J=3.3 Hz), 53.2 (d, J=2.4 Hz), 51.4, 51.3, 43.8, 43.5, 40.3, 34.0, 30.5, 30.4, 29.7, 29.2 (t, J=22.1 Hz), 28.9 (t, J=23.2 Hz), 28.4, 23.4, 5.6, 5.4. C-35 is a new compound.

[0153] Embodiment 40

[0154]

[0155] Into a 25 mL quartz reaction tube replaced with argon five times, 128.0 mg (0.6 mmol) of compound A-28 and 103.8 mg (0.3 mmol) of compound B-2 were injected. After irradiation with 470-475 nm blue light for 10 min, compound C-36 was obtained with a yield of 68% (dr = 3.5:1). The ratio of trans: cis is in brackets. Trans: 1 H NMR (400MHz, CDCl3) δ7.36–7.31(m,1H),7.26–7.18(m,3H),4.35–4.31(m,1H),3.22–2. 98(m,5H),2.87–2.79(m,1H),2.76–2.56(m,3H),2.54–2.48(m,1H),2.36–2.02(m,4H). 19 F NMR(376MHz, CDCl3)δ-81.04–-81.09(m,3F),-112.76(dm,J=272.2Hz,1F),-11 5.04(dm,J=273.4Hz,1F),-124.42–-124.51(m,2F),-125.91–-126.03(m,2F). 13C NMR (101 MHz, CDCl3) δ 144.0, 144.0, 142.7, 127.6, 126.1, 126.1, 125.2, 124.8, 124.8, 120–110 (m), 66.2, 66.1, 56.4, 56.0, 54.9 (d, J = 3.3 Hz), 54.5 (d, J = 3.3 Hz), 43.4, 43.3, 33.9 (d, J = 2.6 Hz), 33.8 (d, J = 2.7 Hz), 30.6, 30.6, 29.2 (t, J = 21.2 Hz), 29.1 (t, J = 21.5 Hz), 27.2, 27.2, 6.0. C-36 is a new compound.

[0156] The reaction temperature in the above examples is 25°C.

[0157] Compounds C-1 to C-36 synthesized in Examples 1 to 40 are all new compounds and have potential applications in medicine, pesticides, and materials science.

[0158] All documents mentioned in the present invention are cited as references in this application, just as each document is cited as reference individually. In addition, it should be understood that after reading the above teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

[0159] It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described below (such as embodiments) can be combined with each other to form a new or preferred technical solution. Due to space limitations, they will not be described one by one here.

[0160] The above is only an embodiment of the present invention. The common knowledge such as the known specific structure and characteristics in the scheme is not described in detail here. For those skilled in the art, several modifications and improvements can be made without departing from the structure of the present invention. These should also be regarded as the protection scope of the present invention. These will not affect the effect of the implementation of the present invention and the practicality of the patent. The protection scope required by this application shall be based on the content of its claims, and the specific implementation methods and other records in the specification can be used to interpret the content of the claims.

Claims

1. A method for synthesizing a fluoroalkyl-substituted pyrrolidine, characterized in that: The steps include: reacting a compound of formula A with a compound of formula B in an inert gas under irradiation with blue light of different wavelengths of 440-475 nm to form a compound of formula C; In the above reaction formula, R in formula A is optionally phenyl, C 1-15 Alkyl substituted phenyl, C 1-15 Alkoxy substituted phenyl, halogen substituted phenyl, cyano substituted phenyl, halogen substituted phenyl, ester substituted phenyl, pyrimidine, quinoline, pyridine, halogen substituted pyridine or indane; or a compound of formula A is selected from , , , , , , , ; R f CF2CO2Et or C n F 2n+1 , where n = 2-8.

2. The method for synthesizing a fluoroalkyl-substituted pyrrolidine according to claim 1, characterized in that: The molar ratio of the compound of formula A to the compound of formula B is 1 to 3:

1.

3. The method for synthesizing a fluoroalkyl-substituted pyrrolidine according to claim 2, characterized in that: The reaction is carried out at 0-50°C.

4. The method for synthesizing a fluoroalkyl-substituted pyrrolidine according to claim 3, characterized in that: An additive base is added during the reaction.

5. The method for synthesizing a fluoroalkyl-substituted pyrrolidine according to claim 4, characterized in that: The additive base is selected from carbonates.

6. The method for synthesizing a fluoroalkyl-substituted pyrrolidine according to claim 5, characterized in that: The additive base is selected from potassium carbonate.

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