A method for preparing an alpha, beta-unsaturated aldehyde based on nickel and visible light synergistic catalysis of propargyl ether rearrangement reaction

Abstract

The application discloses a method for preparing alpha, beta-unsaturated aldehyde based on nickel and visible light synergistic catalysis propargyl ether rearrangement reaction, which comprises the following steps: in the presence of a nickel catalyst, a ligand, a photocatalyst and a base and under the condition of blue light irradiation, propargyl ether of formula (1) is reacted with bromide of formula (2) in an organic solvent to generate alpha, beta-unsaturated aldehyde compound of formula (3). The preparation method has the advantages of cheap and easily available reaction raw materials, simple reaction operation, wide application range of reaction substrates, easy reaction amplification, mild reaction conditions and the like, and can realize industrial production and application.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, and particularly relates to a method for preparing alpha, beta-unsaturated aldehyde based on synergistic catalysis of nickel and visible light on propargyl ether rearrangement reaction. BACKGROUND

[0002] In organic synthesis, alpha, beta-unsaturated aldehyde is a very important class of synthons, which can be obtained by oxidation reaction to obtain alpha, beta-unsaturated acid, by reduction reaction to obtain saturated alkyl aldehyde and allyl alcohol, by epoxidation reaction to obtain epoxide compound, and by cyclization reaction to obtain chroman compounds. Meanwhile, alpha, beta-unsaturated aldehyde also has good pharmacological activity, such as anti-tumor activity, anti-inflammatory activity, anti-fungal and bacterial activity, etc.

[0003] The 1,4-aryl migration rearrangement reaction of propargyl ether is a very efficient and simple method for obtaining alpha, beta-unsaturated aldehyde compounds. In 2017, Liu's group reported a synthesis method of alpha, beta-unsaturated aldehyde compounds based on 1,4-aryl migration strategy (C.-H. Guo, D.-Q. Chen, S. Chen, X.-Y. Liu, Adv. Synth. Catal. 2017, 359, 2901-2906.), which discloses a 1,4-aryl migration rearrangement reaction of propargyl ether using AgSCF3 as a free radical precursor and K2S2O8 as an oxidant, and the reaction process is shown in the following equation:

[0004]

[0005] However, the technology has obvious defects: first, the reaction can only use AgSCF3 as a free radical precursor, so that only alpha, beta-unsaturated aldehyde containing SCF3 can be obtained; second, the reaction needs excessive K2S2O8 as an oxidant, so that the reaction is not redox neutral condition, and the atomic economy of the reaction is poor; third, the reaction is not a catalytic method. SUMMARY

[0006] The present application provides a preparation method of alpha, beta-unsaturated aldehyde compounds, which first uses simple and readily available propargyl ether and bromide as reaction substrates, and realizes the synthesis of multiple types of alpha, beta-unsaturated aldehyde compounds by synergistic catalysis of nickel and visible light.

[0007] The technical scheme of the present application is as follows:

[0008] A method for preparing an α,β-unsaturated aldehyde based on nickel and visible light synergistic catalysis of propargyl ether rearrangement reaction, comprising: under the conditions of a nickel catalyst, a ligand, a photocatalyst, a base and blue light irradiation, a compound of formula (1) and a compound of formula (2) are reacted in an organic solvent to generate an α,β-unsaturated aldehyde compound of formula (3):

[0009]

[0010] Preferably, the compound of formula (1) is selected from:

[0011]

[0012]

[0013] Preferably, the compound of formula (2) is selected from:

[0014]

[0015]

[0016] Preferably, the photocatalyst is selected from:

[0017]

[0018] Preferably, the nickel catalyst is selected from:

[0019] NiCl2, Ni(acac)2, NiBr2, ethylene glycol dimethyl ether nickel bromide (NiBr2-glyme), Ni(OAc)2.

[0020] Preferably, the ligand is selected from:

[0021]

[0022] Preferably, the base is selected from:

[0023] Sodium carbonate (Na2CO3), potassium carbonate (K2CO3), cesium carbonate (Cs2CO3), sodium bicarbonate (NaHCO3), potassium bicarbonate (KHCO3), potassium phosphate (K3PO4), dipotassium hydrogen phosphate (K2HPO4).

[0024] Preferably, the wavelength of the blue light is 390-440 nm; further preferably 390 nm or 427 nm or 440 nm.

[0025] Preferably, the reaction is carried out in an organic solvent, and the organic solvent is at least one of acetonitrile, acetone, toluene, ethyl acetate, tetrahydrofuran, ethylene glycol dimethyl ether, 1,2-dichloroethane, 1,4-dioxane, dimethyl sulfoxide.

[0026] Preferably, the molar ratio of the compound of formula (1), the compound of formula (2), the nickel catalyst, the photocatalyst is 1:1.0-2.5:0.05-0.15:0.01-0.05.

[0027] The reaction temperature is room temperature; preferably, the reaction temperature is 25-30℃.

[0028] The α,β-unsaturated aldehyde compound prepared by the present application is a very important organic synthesis intermediate, which can be converted into various organic compounds through various chemical reactions.

[0029] Compared with the prior art, the present application has the following beneficial effects:

[0030] (1) The present application first uses simple and readily available propargyl ether and bromide as reaction substrates, and realizes the synthesis of various α,β-unsaturated aldehyde compounds by nickel and visible light synergistic catalysis.

[0031] (2) The preparation method provided by the present application can be applied to bromo ester, bromo amide, bromo thioester, bromo ester derived from drug molecules, and bromo ester derived from sugar molecules, and has the advantages of simple and readily available substrates and wide applicability.

[0032] (3) The preparation method of the present application has the advantages of inexpensive and readily available reaction raw materials, simple reaction operation, wide application range of reaction substrates, easy reaction scale-up, and mild reaction conditions, and can realize industrial production and application. DETAILED DESCRIPTION

[0033] The present application will be further described in detail below in combination with examples, and it should be pointed out that the following examples are intended to facilitate the understanding of the present application and do not limit the present application in any way.

[0034] The operation methods not specified in the following examples are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturers. Unless otherwise specified, the mol% amount of the nickel catalyst and the photocatalyst in each example is based on compound 1.

[0035] In the following examples, the photocatalyst is:

[0036]

[0037] In the following examples, the ligand is:

[0038]

[0039] Example 1: Effect of PC1 and L1 on the reaction

[0040]

[0041] In a glove box, NiBr2-glyme (10 mol%), L1 (12 mol%), PC1 (3 mol%), KHCO3 (0.2 mmol), alkyne 1 (0.1 mmol) were weighed into a 4 mL vial, solvent MeCN (1.0 mL), ethyl bromoacetate 2 (0.2 mmol) were added successively, and the PTFE cap was screwed tightly. The vial was taken out of the glove box and placed under a blue light at 440 nm. The reaction was carried out at 25 °C for 12 h. After the reaction was completed, the solvent was removed by rotary evaporation to give the crude product. The conversion and yield of the reaction were analyzed by thin layer chromatography or nuclear magnetic resonance. The experimental results were as follows: the nuclear magnetic yield was 52%.

[0042] Example 2: Effect of PC2 on the reaction

[0043] The difference from Example 1 is only that PC2 is used instead of PC1 in an equimolar amount, and the rest is the same. The experimental results are as follows: the nuclear magnetic yield is 12%.

[0044] Example 3: Effect of PC3 on the reaction

[0045] The difference from Example 1 is only that PC3 is used instead of PC1 in an equimolar amount, and the rest is the same. The experimental results are as follows: the nuclear magnetic yield is 21%.

[0046] Example 4: Effect of PC4 on the reaction

[0047] The difference from Example 1 is only that PC4 is used instead of PC1 in an equimolar amount, and the rest is the same. The experimental results are as follows: the nuclear magnetic yield is 35%.

[0048] Example 5: Effect of PC5 on the reaction

[0049] The difference from Example 1 is only that PC5 is used instead of PC1 in an equimolar amount, and the rest is the same. The experimental results are as follows: the nuclear magnetic yield is 45%.

[0050] Example 6: Effect of PC6 on the reaction

[0051] The difference from Example 1 is only that PC6 is used instead of PC1 in an equimolar amount, and the rest is the same. The experimental results are as follows: the nuclear magnetic yield is 32%.

[0052] Example 7: Effect of L2 on the reaction

[0053] The difference from Example 1 is only that L2 is used instead of L1 in an equimolar amount, and the rest is the same. The experimental results are as follows: the nuclear magnetic yield is 30%.

[0054] Example 8: Effect of L3 on the reaction

[0055] The difference from Example 1 is only that L3 is used instead of L1 in an equimolar amount, and the rest is the same, the resulting experimental results: the yield of nuclear magnetic resonance is 29%.

[0056] Example 9: Effect of L4 on the reaction

[0057] The difference from Example 1 is only that L4 is used instead of L1 in an equimolar amount, and the rest is the same, the resulting experimental results: the yield of nuclear magnetic resonance is 45%.

[0058] Example 10: Effect of L5 on the reaction

[0059] The difference from Example 1 is only that L5 is used instead of L1 in an equimolar amount, and the rest is the same, the resulting experimental results: the yield of nuclear magnetic resonance is 30%.

[0060] Example 11: Effect of L6 on the reaction

[0061] The difference from Example 1 is only that L6 is used instead of L1 in an equimolar amount, and the rest is the same, the resulting experimental results: the yield of nuclear magnetic resonance is 35%.

[0062] Example 12: Effect of L7 on the reaction

[0063] The difference from Example 1 is only that L7 is used instead of L1 in an equimolar amount, and the rest is the same, the resulting experimental results: the yield of nuclear magnetic resonance is 10%.

[0064] Example 13: Effect of L8 on the reaction

[0065] The difference from Example 1 is only that L8 is used instead of L1 in an equimolar amount, and the rest is the same, the resulting experimental results: the yield of nuclear magnetic resonance is 15%.

[0066] Example 14: Effect of NiCl2 on the reaction

[0067] The difference from Example 1 is only that NiCl2 is used instead of NiBr2-glyme in an equimolar amount, and the rest is the same, the resulting experimental results: the yield of nuclear magnetic resonance is 46%.

[0068] Example 15: Effect of Ni(acac)2 on the reaction

[0069] The difference from Example 1 is only that Ni(acac)2 is used instead of NiBr2-glyme in an equimolar amount, and the rest is the same, the resulting experimental results: the yield of nuclear magnetic resonance is 37%.

[0070] Example 16: Effect of NiBr2 on the reaction

[0071] The difference from Example 1 is only that NiBr2 is used instead of NiBr2-glyme in an equimolar amount, and the rest is the same, the resulting experimental results: the yield of nuclear magnetic resonance is 50%.

[0072] Example 17: Effect of Ni(OAc)2 on the reaction

[0073] The difference from Example 1 is only that Ni(OAc)2 is used instead of NiBr2-glyme in an equimolar amount, and the rest is the same. The experimental results obtained are: NMR yield is 12%.

[0074] Example 18: Effect of Na2CO3 on the reaction

[0075] The difference from Example 1 is only that Na2CO3 is used instead of KHCO3 in an equivalent amount, and the rest is the same. The experimental results obtained are: NMR yield is 28%.

[0076] Example 19: Effect of K2CO3 on the reaction

[0077] The difference from Example 1 is only that K2CO3 is used instead of KHCO3 in an equivalent amount, and the rest is the same. The experimental results obtained are: NMR yield is 25%.

[0078] Example 20: Effect of Cs2CO3 on the reaction

[0079] The difference from Example 1 is only that Cs2CO3 is used instead of KHCO3 in an equivalent amount, and the rest is the same. The experimental results obtained are: NMR yield is 40%.

[0080] Example 21: Effect of NaHCO3 on the reaction

[0081] The difference from Example 1 is only that NaHCO3 is used instead of KHCO3 in an equivalent amount, and the rest is the same. The experimental results obtained are: NMR yield is 39%.

[0082] Example 22: Effect of K3PO4 on the reaction

[0083] The difference from Example 1 is only that K3PO4 is used instead of KHCO3 in an equivalent amount, and the rest is the same. The experimental results obtained are: NMR yield is 31%.

[0084] Example 23: Effect of K2HPO4 on the reaction

[0085] The difference from Example 1 is only that K2HPO4 is used instead of KHCO3 in an equivalent amount, and the rest is the same. The experimental results obtained are: NMR yield is 5%.

[0086] Example 24: Effect of 427 nm blue light on the reaction

[0087] The difference from Example 1 is only that the wavelength of the blue light is 427 nm, and the rest is the same. The experimental results obtained are: NMR yield is 45%.

[0088] Example 25: Effect of 390 nm blue light on the reaction

[0089] The difference with Example 1 is only the blue light wavelength is 390 nm, the rest is the same, the resulting experimental results: NMR yield is 22%.

[0090] Example 26: Effect of EA solvent on the reaction

[0091] The difference with Example 1 is only the solvent MeCN is replaced with an equal volume of EA, the rest is the same, the resulting experimental results: NMR yield is 15%.

[0092] Example 27: Effect of DMSO solvent on the reaction

[0093] The difference with Example 1 is only the solvent MeCN is replaced with an equal volume of DMSO, the rest is the same, the resulting experimental results: NMR yield is 26%.

[0094] Example 28: Effect of Acetone solvent on the reaction

[0095] The difference with Example 1 is only the solvent MeCN is replaced with an equal volume of Acetone, the rest is the same, the resulting experimental results: NMR yield is 22%.

[0096] Example 29: Effect of Toluene solvent on the reaction

[0097] The difference with Example 1 is only the solvent MeCN is replaced with an equal volume of Toluene, the rest is the same, the resulting experimental results: NMR yield is 6%.

[0098] Example 30: Effect of THF solvent on the reaction

[0099] The difference with Example 1 is only the solvent MeCN is replaced with an equal volume of THF, the rest is the same, the resulting experimental results: NMR yield is 18%.

[0100] Example 31: Effect of ethylene glycol dimethyl ether solvent on the reaction

[0101] The difference with Example 1 is only the solvent MeCN is replaced with an equal volume of ethylene glycol dimethyl ether, the rest is the same, the resulting experimental results: NMR yield is 8%.

[0102] Example 32: Effect of 1,2-dichloroethane solvent on the reaction

[0103] The difference with Example 1 is only the solvent MeCN is replaced with an equal volume of 1,2-dichloroethane, the rest is the same, the resulting experimental results: NMR yield is 9%.

[0104] Example 33: Effect of 1,4-dioxane solvent on the reaction

[0105] The difference from Example 1 is only that the solvent MeCN is replaced with equal volume of 1,4-dioxane, and the rest is the same. The obtained experimental results: NMR yield is 6%.

[0106] Example 34: Investigation of propargyl ether and bromide reaction substrates

[0107]

[0108] In the glove box, NiBr2-glyme (10 mol%), L1 (12 mol%), PC1 (3 mol%), KHCO3 (0.4 mmol), propargyl ether (0.2 mmol) were weighed into a 4 mL sample bottle, and solvent MeCN (2.0 mL), bromide (0.4 mmol) were added in turn, and the PTFE cap was screwed tightly. The sample bottle was taken out of the glove box and placed under 440 nm blue light, and reacted at 25 °C for 12 hours. After the reaction was completed, the crude product was obtained after the solvent was removed by rotary evaporation. Thin layer chromatography or nuclear magnetic resonance was used to analyze the conversion rate and separation yield of the reaction, and the obtained experimental results are shown in Table 1.

[0109] Table 1 Investigation of propargyl ether and bromide reaction substrates

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117] The analytical data of compound 4-46 are as follows:

[0118] Analytical data of α,β-unsaturated aldehyde 4

[0119] 1 H NMR (600 MHz, Chloroform-d) δ 9.58 (s, 1H), 7.44-7.34 (m, 7H), 7.21 (dt, J = 6.4, 1.8 Hz, 5H), 4.15 (q, J = 7.1 Hz, 2H), 3.41 (s, 2H), 1.25 (t, J = 7.1 Hz, 3H).

[0120] 13C NMR (151 MHz, CDC13) δ 192.99, 171.34, 161.72, 140.25, 138.29, 132.98, 131.24, 129.50, 129.18, 129.14, 128.51, 128.20, 60.90, 34.43, 14.16.

[0121] HRMS (ESI) m / z [M + H] + calcd for C 19 H 19 O3: 295.1329, found: 295.1330

[0122] Analytical data of a, b-unsaturated aldehyde 5

[0123] 1 Hc NMR (600 MHz, CDC13) δ 9.66 (s, 0.76H), 9.59 (s, 0.89H), 7.63-7.56 (m, 7.40H), 7.48-7.34 (m, 10.94H), 7.32-7.23 (m, 7.75H), 4.17 (p, J = 7.2 Hz, 3.94H), 3.48 (s, 2H), 3.43 (s, 1.68H), 1.26 (dt, J = 7.2, 3.6 Hz, 5.83H).

[0124] 13 C NMR (151 MHz, CDC13) δ 192.94, 192.89, 171.40, 171.35, 161.41, 161.33, 142.44, 142.08, 140.25, 140.15, 140.05, 139.14, 138.33, 137.18, 133.09, 133.03, 131.84, 131.36, 129.79, 129.58, 129.25, 128.95, 128.93, 128.56, 128.25, 127.90, 127.84, 127.14, 127.10, 126.84, 60.95, 60.92, 34.58, 34.56, 14.19.

[0125] HRMS (ESI) m / z [M + H] + calcd for C 25 H 23 O3: 371.1642, found: 371.1641.

[0126] Analytical data of a, b-unsaturated aldehyde 6

[0127] 1H NMR (600 MHz, CDC13) δ 9.58 (s, 0.82H), 9.54 (s, 0.94H), 7.37 (t, J = 3.2 Hz, 5.62H), 7.21 (dt, J = 8.6, 2.0 Hz, 7.48H), 7.12 (dd, J = 8.2, 3.7 Hz, 3.91H), 4.19 - 4.12 (m, 3.76H), 3.44 (s, 2H), 3.39 (s, 1.76H), 2.93 (dp, J = 9.3, 6.9 Hz, 1.96H), 1.26 (dd, J = 7.0, 3.6 Hz, 17.33H).

[0128] 13 C NMR (151 MHz, CDC13) δ 193.14, 193.09, 171.46, 171.40, 161.95, 161.87, 150.65, 150.22, 140.44, 138.61, 137.65, 135.69, 132.71, 132.67, 131.41, 131.32, 129.40, 129.33, 129.20, 129.08, 128.44, 128.11, 126.52, 126.24, 60.85, 34.55, 34.53, 33.94, 23.79, 14.16.

[0129] HRMS (ESI) m / z [M + H] + calcd for C 22 H 25 O3: 337.1798, found: 337.1796.

[0130] Analytical data for a, b-unsaturated aldehyde 7

[0131] 1 H NMR (600 MHz, CDC13) δ 9.51 (s, 0.83H), 9.46 (s, 0.89H), 7.36 - 7.25 (m, 9.09H), 7.14 (dq, J = 7.1, 1.8 Hz, 3.69H), 7.08 - 7.01 (m, 3.70H), 4.07 (dd, J = 9.6, 7.1 Hz, 3.74H), 3.37 (s, 2H), 3.32 (s, 1.75H), 1.25 (d, J = 4.3 Hz, 16.9H), 1.19 - 1.17 (m, 5.66H).

[0132] 13C NMR (151 MHz, CDCI3) δ 193.14, 193.08, 171.44, 171.38, 161.86, 161.79, 152.92, 152.51, 140.43, 138.61, 137.25, 135.30, 132.75, 132.70, 131.29, 131.13, 129.37, 129.18, 129.06, 128.44, 128.11, 125.36, 125.09, 60.84, 60.82, 34.78, 34.76, 34.55, 34.52, 31.22, 29.69, 14.17, 14.15.

[0133] HRMS (ESI) m / z [M + H] + calcd for C 23 H 27 O3: 351.1955, found: 351.1954.

[0134] Analytical data of a, b-unsaturated aldehyde 8

[0135] 1 H NMR (600 MHz, CDCI3) δ 9.55 (d, J = 13.2 Hz, 1 H), 7.46 - 7.34 (m, 3H), 7.24 - 7.16 (m, 4H), 7.10 - 7.02 (m, 2H), 4.19 - 4.11 (m, 2H), 3.40 (d, J = 1.9 Hz, 2H), 1.26 (td, J = 7.1, 5.5 Hz, 3H).

[0136] 13 C NMR (151 MHz, CDCI3) δ 192.87, 192.63, 171.36, 171.32, 164.38, 164.02, 162.72, 162.36, 160.66, 160.51, 140.04, 138.14, 136.26, 136.23, 134.32, 134.29, 133.21, 133.15, 133.06, 131.30, 131.25, 129.73, 129.42, 129.19, 128.61, 128.31, 115.74, 115.60, 115.48, 115.34, 61.04, 60.98, 34.54, 34.51, 14.16.

[0137] 19 F NMR (565 MHz, CDCI3) δ -75.99, -110.94, -111.33, -111.35.

[0138] HRMS (ESI) m / z [M + H] + calcd for C 19 H 18 FO3: 313.1235, found: 313.1234.

[0139] Analytical data of a, b-unsaturated aldehyde 9

[0140] 1 H NMR (600 MHz, CDC13) δ 9.57 (s, 0.77H), 9.55 (s, 0.82H), 7.46 - 7.32 (m, 8.64H), 7.22 - 7.10 (m, 7.14H), 4.15 (qd, J = 7.1, 4.7 Hz, 3.81H), 3.40 (s, 2H), 3.39 (s, 1.95H), 1.25 (td, J = 7.1, 5.5 Hz, 6.58H).

[0141] 13 C NMR (151 MHz, CDC13) δ 192.67, 192.39, 171.17, 160.29, 160.19, 139.83, 138.63, 137.85, 136.71, 135.86, 135.43, 133.45, 133.26, 132.46, 131.22, 130.56, 129.73, 129.42, 129.12, 128.84, 128.64, 128.54, 128.33, 61.02, 60.96, 34.45, 34.41, 14.15.

[0142] HRMS (ESI) m / z [M + H] + calcd for C 19 H 18 ClO3: 329.0939, found: 329.0935.

[0143] Analytical data of a, b-unsaturated aldehyde 10

[0144] 1H NMR (600 MHz, CDC13) δ 9.58 (s, 0.51H), 9.50 (s, 0.96H), 7.44 - 7.33 (m, 4.49H), 7.20 (dt, J=6.9, 2.4 Hz, 3.16H), 7.16 - 7.09 (m, 3.28H), 6.87 (dd, J=8.8, 2.0 Hz, 3.21H), 4.15 (dq, J=14.1, 7.1 Hz, 3.65H), 4.06 (p, J=7.0 Hz, 3.77H), 3.46 (s, 2H), 3.38 (s, 1.18H), 1.43 (td, J=7.0, 5.3 Hz, 5.38H), 1.26 (dt, J=10.3, 7.2 Hz, 7.34H).

[0145] 13 C NMR (151 MHz, CDC13) δ 193.11, 193.01, 171.60, 171.52, 161.83, 161.63, 160.38, 159.93, 140.55, 138.82, 133.09, 132.43, 132.25, 132.20, 131.47, 131.09, 129.48, 129.40, 129.17, 128.43, 128.10, 114.31, 114.07, 63.64, 63.58, 60.87, 60.83, 34.71, 14.75, 14.18.

[0146] HRMS (ESI) m / z [M + H] + calcd for C 21 H 23 O4: 339.1591, found: 339.1589.

[0147] Analytical data for a, b-unsaturated aldehyde 11

[0148] 1 H NMR (600 MHz, CDC13) δ 9.60 (s, 0.98H), 9.55 (s, 0.90H), 7.65 (dd, J=8.3, 2.9 Hz, 3.98H), 7.47 - 7.32 (m, 10.07H), 7.24 - 7.16 (m, 4.03H), 4.15 (qd, J=7.1, 2.8 Hz, 4.18H), 3.43 (s, 2H), 3.37 (s, 2.11H), 1.26 (t, J=7.1 Hz, 6.89H).

[0149] 13C NMR (151 MHz, CDCI3) δ 192.48, 192.13, 171.02, 159.73, 143.70, 141.87, 139.48, 137.38, 134.06, 133.75, 131.22 (p, J = 33 Hz), 131.30, 131.09, 129.83, 129.51, 129.41, 128.96, 128.75, 128.46, 125.59, 125.56, 125.27, 123.84 (q, J = 272.5 Hz), 61.09, 61.03, 34.29, 34.24, 14.12.

[0150] 19 F NMR (565 MHz, CDCI3) δ -62.80.

[0151] HRMS (ESI) m / z [M + H] + calcd for C 20 H 17 F3O3: 363.1203, found: 363.1207.

[0152] Analytical data for a, b-unsaturated aldehyde 12

[0153] 1 H NMR (600 MHz, CDCI3) δ 9.49 (s, 1 H), 7.38 - 7.28 (m, 3 H), 7.22 - 7.08 (m, 6 H), 4.08 (qd, J = 7.1, 3.5 Hz, 2 H), 3.33 (d, J = 7.3 Hz, 2 H), 1.18 (td, J = 7.2, 3.9 Hz, 3 H).

[0154] 13 C NMR (151 MHz, CDCI3) δ 192.61, 192.32, 171.16, 171.11, 159.98, 159.88, 150.08, 149.74, 139.77, 138.68, 137.82, 136.78, 133.66, 133.46, 132.64, 131.16, 130.80, 129.74, 129.43, 129.05, 128.67, 128.38, 120.76, 120.47, 120.40 (q, J = 257.7 Hz), 61.03, 60.96, 34.41, 34.35, 14.10.

[0155] 19 F NMR (565 MHz, CDCI3) δ -57.71.

[0156] HRMS (ESI) m / z [M + H] + calcd for C 20 H 18 F3O4: 379.1152, found: 379.1148.

[0157] Analytical data of α,β-unsaturated aldehyde 13

[0158] 1 H NMR (600 MHz, CDC13) δ 9.60 (s, 1H), 9.56 (s, 0.93H), 8.12 - 7.97 (m, 4.06H), 7.45 - 7.34 (m, 6.14H), 7.32 - 7.28 (m, 4.10H), 7.22 - 7.15 (m, 4.10H), 4.15 (qd, J = 7.2, 3.3 Hz, 4.07H), 3.93 (s, 2.96H), 3.92 (s, 3.21H), 3.42 (s, 2H), 3.36 (s, 2.15H), 1.25 (dd, J = 5.4, 2.4 Hz, 6.65H).

[0159] 13 C NMR (151 MHz, CDC13) δ 192.88, 192.69, 171.37, 171.32, 161.20, 161.10, 141.30, 140.78, 140.20, 138.34, 136.64, 134.67, 132.85, 132.78, 131.76, 131.37, 129.77, 129.75, 129.56, 129.28, 129.24, 128.51, 128.20, 125.73, 125.42, 60.92, 60.87, 34.57, 15.17, 14.16.

[0160] HRMS (ESI) m / z [M + H] + calcd for C 20 H 21 O3S: 341.1206, found: 341.1211.

[0161] Analytical data of α,β-unsaturated aldehyde 14

[0162] 1H NMR (600 MHz, CDC13) δ 9.59 (s, 1.62H), 9.54 (s, 0.85H), 7.69 (dd, J = 8.2, 3.6 Hz, 5.98H), 7.49 - 7.33 (m, 15.16H), 7.22 - 7.13 (m, 5.56H), 4.15 (q, J = 7.1 Hz, 5.95H), 3.42 (s, 2H), 3.34 (s, 3.76H), 1.26 (td, J = 7.1, 2.7 Hz, 8.64H).

[0163] 13 C NMR (151 MHz, CDC13) δ 192.29, 191.76, 170.89, 159.14, 159.08, 144.60, 142.85, 139.10, 136.94, 134.40, 133.94, 132.39, 132.02, 131.58, 131.07, 130.01, 129.76, 129.69, 128.93, 128.86, 128.58, 118.22, 118.12, 113.26, 112.98, 61.21, 61.11, 34.30, 34.22, 14.13.

[0164] HRMS (ESI) m / z [M + H] + calcd for C 20 H 17 NO3: 371.1642, not found.

[0165] Analytical data for a, b-unsaturated aldehyde 15

[0166] 1 H NMR (600 MHz, CDC13) δ 9.57 (s, 1H), 9.52 (s, 1H), 7.70 - 7.48 (m, 6H), 7.46 - 7.32 (m, 6H), 7.22 - 7.10 (m, 9H), 4.15 (p, J = 7.2 Hz, 4H), 3.43 (s, 2H), 3.39 (s, 2H), 2.18 (d, J = 2.7 Hz, 6H), 1.25 (q, J = 7.0 Hz, 10H).

[0167] 13C NMR (151 MHz, CDC13) δ 192.05, 191.92, 170.50, 167.61, 160.41, 139.14, 138.57, 138.10, 137.32, 134.79, 132.78, 131.67, 131.27, 130.36, 129.29, 128.60, 128.28, 127.50, 127.19, 118.39, 118.06, 59.98, 59.92, 33.61, 23.58, 13.13.

[0168] HRMS (ESI) m / z [M + H] + calcd for C 21 H 22 NO4: 352.1543, found: 342.1540.

[0169] Analytical data for a, b-unsaturated aldehyde 16

[0170] 1 H NMR (600 MHz, CDC13) δ 9.59 (s, 0.79H), 9.53 (s, 0.94H), 7.44-7.33 (m, 5.40H), 7.23-7.18 (m, 7.12H), 7.15-7.08 (m, 3.62H), 4.15 (dq, J = 9.6, 7.1 Hz, 3.70H), 3.43 (s, 2H), 3.39 (s, 1.71H), 2.50 (s, 2.56H), 2.49 (s, 3H), 1.26 (dt, J = 8.5, 7.2 Hz, 5.71H).

[0171] 13 C NMR (151 MHz, CDC13) δ 192.53, 192.29, 171.05, 170.99, 166.45, 166.39, 160.26, 160.22, 144.60, 142.74, 139.61, 137.50, 133.84, 133.56, 131.09, 131.05, 130.98, 130.70, 129.78, 129.73, 129.42, 129.06, 128.97, 128.67, 128.38, 61.03, 60.98, 52.31, 52.27, 34.29, 34.27, 14.13.

[0172] HRMS (ESI) m / z [M + H] + calcd for C 21 H 21O5: 353.1384, found: 353.1385.

[0173] Analytical data for a, b-unsaturated aldehyde 17

[0174] 1 H NMR (600 MHz, CDC13) δ 9.60 (s, 1H), 9.56 (s, 0H), 7.96 (d, J = 1.9 Hz, 1H), 7.45 - 7.28 (m, 5H), 7.19 (td, J = 4.2, 2.4 Hz, 2H), 4.15 (qd, J = 7.1, 1.6 Hz, 2H), 3.42 (s, 1H), 3.37 (s, 1H), 2.62 (s, 2H), 2.61 (s, 2H), 1.25 (t J = 7.2 Hz, 4H).

[0175] 13 C NMR (151 MHz, CDC13) δ 197.33, 197.28, 192.48, 192.21, 171.03, 170.97, 160.16, 160.09, 144.71, 142.87, 139.56, 137.56, 137.46, 137.35, 133.91, 133.59, 131.28, 131.07, 129.75, 129.43, 129.30, 128.95, 128.70, 128.49, 128.41, 128.13, 61.04, 60.99, 34.28, 26.61, 14.13.

[0176] HRMS (ESI) m / z [M + H] + calcd for C 21 H 21 O4: 337.1435, found: 337.1439.

[0177] Analytical data for a, b-unsaturated aldehyde 18

[0178] 1 H NMR (600 MHz, CDC13) δ 9.57 (s, 0.90H), 9.57 (s, 0.91H), 7.46 - 7.29 (m, 9.99H), 7.16 (ddt, J = 44.6, 7.5, 1.7 Hz, 7.85H), 4.15 (qd, J = 7.1, 5.4 Hz, 4.03H), 3.40 (s, 2H), 3.38 (s, 1.98H), 1.26 (q, J = 7.0 Hz, 7H).

[0179] 13C NMR (151 MHz, CDC13) δ 192.61, 192.37, 171.08, 171.03, 159.86, 141.90, 140.02, 139.55, 137.51, 134.64, 134.48, 133.72, 133.53, 131.13, 130.76, 129.87, 129.77, 129.56, 129.47, 129.44, 129.33, 129.25, 129.00, 128.69, 128.39, 127.18, 61.06, 60.99, 34.32, 14.17, 14.15.

[0180] HRMS (ESI) m / z [M + H]+calcd for C + calcd for C 19 H 18 C103: 329.0939, found: 329.0935.

[0181] Analytical data of a, b-unsaturated aldehyde 19

[0182] 1 H NMR (600 MHz, CDC13) δ 9.59 (s, 0.88H), 9.57 (s, 0.88H), 7.43-7.35 (m, 6.14H), 7.31-7.26 (m, 2.18H), 7.24-7.20 (m, 4.05H), 6.97-6.70 (m, 6.20H), 4.15 (q, J = 7.2 Hz, 4.21H), 3.77 (s, 3.03H), 3.76 (s, 2.89H), 3.42 (s, 2H), 3.40 (s, 2H), 1.27-1.24 (m, 7.68H).

[0183] 13 C NMR (151 MHz, CDC13) δ 192.96, 171.36, 161.60, 161.42, 159.56, 159.36, 157.75, 141.55, 140.01, 139.63, 138.08, 133.03, 132.98, 131.15, 129.60, 129.51, 129.20, 129.00, 128.50, 128.18, 123.79, 121.50, 116.61, 114.95, 114.85, 114.47, 60.91, 55.33, 55.27, 34.49, 34.33, 14.15.

[0184] HRMS (ESI) m / z [M + H]+calcd for C + calcd for C20 H 21 O4: 325.1435, found: 325.1430.

[0185] Analytical data for a, b-unsaturated aldehyde 20

[0186] 1 H NMR (600 MHz, CDC13) δ 9.51 (s, 0.85H), 7.40 (dt, J = 30.4, 7.4 Hz, 2.83H), 7.22 (d, J = 7.2 Hz, 1.97H), 6.86 - 6.82 (m, 1.92H), 6.74 (dd, J = 8.4, 2.0 Hz, 0.92H), 4.16 (q, J = 7.1 Hz, 2H), 3.90 (s, 3H), 3.78 (s, 2.99H), 3.47 (s, 1.96H), 1.27 (t, J = 7.2 Hz, 4.32H).

[0187] 13 C NMR (151 MHz, CDC13) δ 193.04, 171.73, 161.92, 149.98, 148.65, 138.54, 132.90, 132.31, 131.47, 129.58, 129.32, 128.44, 128.10, 122.80, 112.59, 110.86, 60.92, 55.91, 55.86, 34.87, 14.17.

[0188] HRMS (ESI) m / z [M + H] + calcd for C 21 H 23 O5: 355.1540, found: 355.1537.

[0189] Analytical data for a, b-unsaturated aldehyde 21

[0190] 1 H NMR (600 MHz, CDC13) δ 9.61 (s, 0.72H), 9.49 (s, 0.82H), 7.43 - 7.32 (m, 4.81H), 7.22 - 7.17 (m, 3.25H), 6.84 (dd, J = 8.5, 2.7 Hz, 1.93H), 6.79 - 6.67 (m, 3.54H), 4.30 - 4.23 (m, 7.01H), 4.19 - 4.10 (m, 3.94H), 3.46 (s, 2H), 3.36 (s, 1.50H), 1.26 (dt, J = 13.4, 7.1 Hz, 5.59H).

[0191] 13 C NMR (151 MHz, CDC13) δ 193.09, 192.96, 171.45, 171.41, 161.40, 161.19, 145.10, 144.66, 143.38, 143.22, 140.31, 138.53, 133.51, 132.51, 132.47, 131.58, 131.34, 129.46, 129.23, 129.14, 128.44, 128.12, 125.14, 122.90, 120.37, 118.59, 117.23, 116.88, 64.49, 64.24, 60.88, 60.83, 34.63, 34.61, 14.17, 14.15.

[0192] HRMS (ESI) m / z [M + H] + Caled for C 21 H 21 O5: 353.1384, found: 353.1380.

[0193] Analytical data for a, b-unsaturated aldehyde 22

[0194] 1 H NMR (600 MHz, CDC13) δ 9.64 (s, 0.83H), 9.62 (s, 0.90H), 7.95 - 7.70 (m, 7.74H), 7.54 (ddd, J = 16.3, 8.2, 5.3 Hz, 3.85H), 7.46 - 7.35 (m, 5.66H), 7.26 (td, J = 4.4, 2.0 Hz, 5.32H), 7.20 (dd, J = 8.5, 1.8 Hz, 0.99H), 4.17 (p, J = 7.4 Hz, 3.67H), 3.48 (s, 2H), 3.47 (s, 1.7H), 1.28 - 1.25 (m, 5.86H).

[0195] 13C NMR (151 MHz, CDCI3) δ 192.97, 171.39, 161.77, 161.70, 140.08, 138.26, 137.65, 135.60, 133.55, 133.51, 133.37, 133.27, 132.87, 132.51, 131.54, 131.40, 129.61, 129.32, 128.74, 128.57, 128.51, 128.45, 128.28, 128.25, 128.08, 127.86, 127.76, 127.30, 127.14, 126.94, 126.72, 126.60, 60.95, 34.57, 14.18.

[0196] HRMS (ESI) m / z [M + H] + calcd for C 23 H 21 O3: 345.1485, found: 345.1484.

[0197] Analytical data of a, b-unsaturated aldehyde 23

[0198] 1 H NMR (600 MHz, CDCI3) δ 9.62 (d, J = 9.6 Hz, 1 H), 7.95 - 7.78 (m, 2H), 7.63 - 7.54 (m, 2H), 7.52 - 7.20 (m, 9H), 4.18 (q, J = 7.1 Hz, 2H), 3.48 (d, J = 2.8 Hz, 2H), 1.29 - 1.25 (m, 4H).

[0199] 13 C NMR (151 MHz, CDCI3) δ 192.98, 171.52, 171.44, 161.91, 161.73, 156.83, 156.80, 156.72, 156.49, 140.53, 138.65, 135.10, 133.13, 131.44, 130.44, 129.69, 129.36, 128.58, 128.27, 127.89, 127.81, 124.60, 124.38, 123.87, 123.68, 123.51, 123.20, 123.12, 121.73, 121.01, 120.84, 111.89, 111.79, 111.52, 60.99, 60.95, 34.73, 34.65, 14.20.

[0200] HRMS (ESI) m / z [M + H] + calcd for C25 H 21 O4: 385.1435, found: 385.1431.

[0201] Analytical data of α,β-unsaturated aldehyde 24

[0202] 1 H NMR (600 MHz, CDC13) δ 9.60 (s, 0.44H), 9.56 (s, 0.50H), 7.44-7.34 (m, 2.98H), 7.26-7.18 (m, 4.13H), 7.07 (dd, J = 8.7, 2.9 Hz, 1.99H), 6.99 (d, J = 7.5 Hz, 1.05H), 6.67-6.58 (m, 2.08H), 4.15 (qd, J = 7.1, 4.2 Hz, 2.01H), 3.98 (td, J = 5.6, 2.3 Hz, 2.09H), 3.42 (d, J = 7.9 Hz, 2H), 2.29 (s, 3.08H), 2.16 (s, 3.09H), 1.93-1.83 (m, 4.26H), 1.38 (d, J = 3.5 Hz, 6.08H), 1.26 (q, J = 6.9 Hz, 3.85H).

[0203] 13 C NMR (151 MHz, CDC13) δ 192.86, 192.67, 192.64, 176.12, 176.04, 171.32, 160.77, 160.63, 156.87, 152.09, 151.73, 140.06, 138.15, 137.59, 136.51, 135.64, 133.27, 133.16, 132.37, 131.34, 130.48, 130.40, 129.66, 129.34, 129.23, 128.58, 128.27, 123.62, 121.71, 121.43, 120.85, 112.03, 67.75, 60.98, 60.93, 42.56, 37.15, 34.53, 29.71, 25.29, 25.13, 21.40, 15.79, 14.17.

[0204] HRMS (ESI) m / z [M + H] + calcd for C 32 H 35 O5: 499.2479, found: 499.2484.

[0205] Analytical data of α,β-unsaturated aldehyde 25

[0206] 1 H NMR (600 MHz, CDC13) δ 9.57 (s, 0.88H), 9.54 (d, J = 1.7 Hz, 1.01H), 7.43 - 7.33 (m, 5.85H), 7.29 (dt, J = 8.4, 2.1 Hz, 3.85H), 7.22 - 7.12 (m, 11.58H), 7.03 (ddd, J = 8.7, 4.3, 2.0 Hz, 3.90H), 4.19 - 4.08 (m, 4.03H), 3.95 (dd, J = 7.1, 3.8 Hz, 2H), 3.40 (t, J = 2.0 Hz, 4H), 2.47 (s, 2.02H), 2.46 (s, 1.92H), 1.86 (hept, J = 6.8 Hz, 2.06H), 1.61 (d, J = 2.5 Hz, 2.93H), 1.60 (d, J = 2.6 Hz, 2.74H), 1.25 (td, J = 7.2, 3.4 Hz, 6.19H), 0.90 (dd, J = 6.7, 1.9 Hz, 11.89H).

[0207] 13 C NMR (151 MHz, CDC13) δ 192.85, 192.82, 192.65, 192.63, 172.98, 172.91, 171.30, 171.24, 160.73, 160.57, 151.95, 151.58, 140.98, 140.03, 138.12, 137.61, 137.00, 135.67, 133.24, 133.14, 132.31, 131.30, 130.41, 129.59, 129.30, 129.19, 128.55, 128.24, 127.21, 121.58, 121.30, 60.96, 60.91, 45.30, 45.05, 34.50, 30.17, 22.39, 18.41, 14.15.

[0208] HRMS (ESI) m / z [M + H] + calcd for C 34 H 39 O6: 543.2741, found: 543.2739.

[0209] Analytical data for a, b-unsaturated aldehyde 26

[0210] 1H NMR (600 MHz, CDC13) δ 9.57 (s, 0.88H), 9.55 (s, 1.02H), 7.45 - 7.33 (m, 9.96H), 7.21 - 7.13 (m, 7.84H), 4.15 (qd, J = 7.1, 4.8 Hz, 4.07H), 3.40 (s, 2H), 3.39 (s, 2.04H), 1.26 (q, J = 6.7 Hz, 6.32H).

[0211] 13 C NMR (151 MHz, CDC13) δ 192.69, 192.41, 171.21, 160.30, 160.21, 139.82, 138.62, 137.85, 136.70, 135.87, 135.43, 133.44, 133.25, 132.47, 131.24, 130.57, 129.74, 129.42, 129.13, 128.84, 128.64, 128.54, 128.33, 61.03, 60.97, 34.47, 34.42, 14.15.

[0212] HRMS (ESI) m / z [M + H] + calcd for C 19 H 18 ClO3: 329.0939, found: 329.0936.

[0213] Analytical data of a, b-unsaturated aldehyde 27

[0214] 1 H NMR (600 MHz, CDC13) δ 9.60 (s, 0H), 9.55 (s, 0H), 7.65 (dd, J = 8.3, 2.8 Hz, 2H), 7.47 - 7.31 (m, 6H), 7.20 (dd, J = 6.5, 2.2 Hz, 2H), 4.15 (qd, J = 7.1, 2.7 Hz, 2H), 3.43 (s, 1H), 3.37 (s, 1H), 1.26 (t J = 7.1 Hz, 4H).

[0215] 13C NMR (151 MHz, CDCI3) δ 192.49, 192.14, 171.03, 171.00, 159.74, 143.70, 141.87, 139.48, 137.38, 134.06, 133.74, 131.31, 131.24 (p, J = 33 Hz), 131.09, 129.84, 129.51, 129.41, 128.96, 128.75, 125.58 (q, J = 3.6 Hz), 125.26 (q, J = 3.2 Hz), 123.83 (q, J = 270 Hz), 61.10, 61.03, 34.29, 34.25, 14.12.

[0216] 19 F NMR (565 MHz, CDCI3) δ -62.80.

[0217] HRMS (ESI) m / z [M + H] + calcd for C 20 H 18 F3O3: 363.1203, found: 363.1201. Analytical data for a, b-unsaturated aldehyde 28

[0218] 1 H NMR (600 MHz, CDCI3) δ 9.66 (s, 0.83 H), 9.59 (s, 0.92 H), 7.60 (d, J = 7.7 Hz, 7.7 H), 7.48 - 7.35 (m, 11.29 H), 7.31 - 7.24 (m, 7.59 H), 4.17 (p, J = 7.3 Hz, 3.89 H), 3.48 (s, 2 H), 3.43 (s, 1.8 H), 1.27 (td, J = 7.1, 2.9 Hz, 6.17 H).

[0219] 13 C NMR (151 MHz, CDCI3) δ 192.96, 192.90, 171.40, 171.35, 161.41, 161.33, 142.44, 142.08, 140.24, 140.15, 140.05, 139.13, 138.32, 137.17, 133.08, 133.02, 131.84, 131.36, 129.79, 129.58, 129.25, 128.94, 128.56, 128.24, 127.89, 127.84, 127.14, 127.10, 126.84, 60.95, 60.92, 34.58, 34.56, 14.18.

[0220] HRMS (ESI) m / z [M + H] + Anal. Calcd for C 25 H 23 O3: 371.1642, found: 371.1641.

[0221] Analytical data of a, b-unsaturated aldehyde 29

[0222] 1 H NMR (600 MHz, CDC13) δ 9.58 (s, 0.69H), 9.50 (s, 0.93H), 7.44-7.34 (m, 4.99H), 7.23-7.10 (m, 6.69H), 6.88 (d, J = 8.2 Hz, 3.30H), 4.15 (dq, J = 14.0, 7.1 Hz, 3.40H), 3.84 (s, 2.32H), 3.82 (s, 2.90H), 3.46 (s, 2H), 3.39 (s, 1.54H), 1.26 (dt, J = 10.3, 7.2 Hz, 5.97H).

[0223] 13 C NMR (151 MHz, CDC13) δ 193.07, 192.95, 171.57, 171.49, 161.73, 161.54, 160.96, 160.52, 140.52, 138.78, 133.06, 132.62, 132.32, 132.28, 131.45, 131.08, 130.67, 129.50, 129.37, 129.19, 128.44, 128.12, 113.86, 113.61, 60.88, 60.83, 55.38, 55.33, 34.69, 14.18.

[0224] HRMS (ESI) m / z [M + H] + Anal. Calcd for C 20 H 21 O4: 325.1435, found: 325.1434.

[0225] Analytical data of a, b-unsaturated aldehyde 30

[0226] 1 H NMR (600 MHz, CDC13) δ 9.63 (s, 1H), 7.49-7.31 (m, 8H), 7.29-7.20 (m, 5H), 7.08 (d, J = 7.9 Hz, 2H), 3.66 (s, 2H).

[0227] 13C NMR (151 MHz, CDC13) δ 192.84, 169.99, 162.35, 150.89, 140.21, 138.15, 132.66, 131.23, 129.66, 129.38, 129.14, 128.67, 128.28, 125.83, 121.55, 115.34, 34.52.

[0228] HRMS (ESI) m / z [M + H] + calcd for C 23 H 19 O3: 343.1329, found: 343.1332.

[0229] Analytical data of a, b-unsaturated aldehyde 31

[0230] 1 H NMR (600 MHz, CDC13) δ 9.57 (s, 1 H), 7.43 - 7.30 (m, 6 H), 7.24 - 7.16 (m, 4 H), 3.34 (s, 2 H), 1.45 (d, J = 1.3 Hz, 9 H).

[0231] 13 C NMR (151 MHz, CDC13) δ 192.99, 170.49, 161.18, 140.39, 138.41, 133.48, 131.19, 129.36, 129.12, 129.06, 128.43, 128.16, 80.88, 35.51, 28.02.

[0232] HRMS (ESI) m / z [M + H] + calcd for C 21 H 23 O3: 323.1642, found: 323.1646.

[0233] Analytical data of a, b-unsaturated aldehyde 32

[0234] 1 H NMR (600 MHz, CDC13) δ 9.54 (s, 1 H), 7.44 - 7.31 (m, 8 H), 7.19 (d, J = 7.5 Hz, 2 H), 6.00 (s, 1 H), 3.30 (s, 2 H), 2.79 (d, J = 4.8 Hz, 3 H).

[0235] 13C NMR (151 MHz, CDCI3) δ 193.52, 170.45, 160.38, 140.55, 138.61, 134.38, 131.30, 129.35, 129.22, 128.91, 128.33, 128.06, 37.41, 35.66, 33.75.

[0236] HRMS (ESI) m / z [M + H] Calcd for C + calcd for C 18 H 18 NO2: 280.1332, found: 280.1334.

[0237] Analytical data of α,β-unsaturated aldehyde 33

[0238] 1 H NMR (600 MHz, CDCI3) δ 9.56 (d, J = 1.8 Hz, 1 H), 7.41 - 7.32 (m, 6H), 7.28 (ddd, J = 5.4, 4.0, 2.1 Hz, 2H), 7.21 - 7.17 (m, 2H), 3.42 (s, 2H), 3.00 (d, J = 1.9 Hz, 3H), 2.97 (d, J = 1.9 Hz, 3H).

[0239] 13 C NMR (151 MHz, CDCI3) δ 193.52, 170.45, 160.38, 140.55, 138.61, 134.38, 131.30, 129.35, 129.22, 128.91, 128.33, 128.06, 37.41, 35.66, 33.75.

[0240] HRMS (ESI) m / z [M + H] Calcd for C + calcd for C 19 H 20 NO2: 294.1489, found: 294.1486.

[0241] Analytical data of α,β-unsaturated aldehyde 34

[0242] 1 H NMR (600 MHz, CDCI3) δ 9.59 (s, 1 H), 7.39 (h, J = 8.4, 7.9 Hz, 6H), 7.30 (d, J = 7.5 Hz, 2H), 7.24 - 7.20 (m, 7H), 3.69 (s, 2H), 3.14 (t, J = 7.8 Hz, 2H), 2.87 (t, J = 7.8 Hz, 2H).

[0243] 13 C NMR (151 MHz, CDCI3) δ 196.88, 192.65, 162.56, 140.04, 138.22, 132.68, 131.20, 129.63, 129.30, 129.08, 128.67, 128.61, 128.49, 128.24, 126.50, 43.54, 35.81, 30.56.

[0244] HRMS (ESI) m / z [M + H] + calcd for C 25 H 23 O2S: 387.1414, not found.

[0245] Analytical data of a, b-unsaturated aldehyde 35

[0246] 1 H NMR (600 MHz, CDCI3) δ 9.58 (s, 1 H), 7.44 - 7.33 (m, 6 H), 7.23 - 7.15 (m, 4 H), 4.12 (t, J = 6.5 Hz, 2 H), 3.41 (s, 2 H), 3.39 (t, J = 6.3 Hz, 2 H), 3.33 (s, 3 H), 1.73 - 1.68 (m, 2 H), 1.65 - 1.61 (m, 2 H).

[0247] 13 C NMR (151 MHz, CDCI3) δ 191.88, 170.30, 160.62, 139.24, 137.29, 131.97, 130.19, 128.46, 128.16, 128.10, 127.50, 127.19, 71.12, 63.72, 57.52, 33.37, 25.04, 24.42.

[0248] HRMS (ESI) m / z [M + H] + calcd for C 22 H 25 O4: 353.1748, found: 353.1754.

[0249] Analytical data of a, b-unsaturated aldehyde 36

[0250] 1H NMR (600 MHz, CDC13) δ 9.58 (s, 1H), 7.45 - 7.32 (m, 6H), 7.24 - 7.17 (m, 4H), 4.71 (td, J = 10.9, 4.4 Hz, 1H), 3.47 - 3.35 (m, 2H), 2.03 - 1.96 (m, 1H), 1.89 (pd, J = 7.0, 2.7 Hz, 1H), 1.67 (ddt, J = 16.8, 6.7, 2.8 Hz, 3H), 1.47 (ddt, J = 12.0, 6.1, 2.8 Hz, 1H), 1.38 - 1.34 (m, 1H), 1.06 (dd, J = 12.8, 3.3 Hz, 1H), 0.97 (q, J = 11.8 Hz, 1H), 0.90 (dd, J = 6.9, 5.1 Hz, 6H), 0.78 (d, J = 7.0 Hz, 3H).

[0251] 13 C NMR (151 MHz, CDC13) δ 192.83, 192.80, 170.79, 140.32, 138.35, 133.10, 131.21, 129.43, 129.13, 128.44, 128.18, 74.80, 47.12, 40.79, 34.62, 34.28, 31.41, 26.16, 23.43, 22.01, 20.80, 16.29.

[0252] HRMS (ESI) m / z [M + H] + calcd for C 27 H 33 O3: 405.2424, found: 405.2426.

[0253] Analytical data for a, b-unsaturated aldehyde 37

[0254] 1 H NMR (600 MHz, CDC13) δ 9.58 (s, 1H), 7.45 - 7.32 (m, 6H), 7.24 - 7.17 (m, 4H), 4.71 (td, J = 10.9, 4.4 Hz, 1H), 3.47 - 3.35 (m, 2H), 2.03 - 1.96 (m, 1H), 1.89 (pd, J = 7.0, 2.7 Hz, 1H), 1.67 (ddt, J = 16.8, 6.7, 2.8 Hz, 3H), 1.47 (ddt, J = 12.0, 6.1, 2.8 Hz, 1H), 1.38 - 1.34 (m, 1H), 1.06 (dd, J = 12.8, 3.3 Hz, 1H), 0.97 (q, J = 11.8 Hz, 1H), 0.90 (dd, J = 6.9, 5.1 Hz, 6H), 0.78 (d, J = 7.0 Hz, 3H).

[0255] 13C NMR (151 MHz, CDC13) δ 192.88, 171.16, 161.88, 147.82, 147.62, 140.16, 138.22, 132.78, 131.24, 129.71, 129.54, 129.22, 129.10, 128.52, 128.20, 122.20, 109.00, 108.23, 101.16, 66.66, 34.38.

[0256] HRMS (ESI) m / z [M + H] + calcd for C 25 H 21 O5: 401.1384, not found.

[0257] Analytical data for a, b-unsaturated aldehyde 38

[0258] 1 H NMR (600 MHz, CDC13) δ 9.58 (s, 1H), 7.35 (ddt, J = 29.1, 14.1, 7.1 Hz, 6H), 7.23 - 7.11 (m, 4H), 6.95 - 6.80 (m, 3H), 5.08 (s, 2H), 3.89 (d, J = 5.1 Hz, 6H), 3.46 (s, 2H).

[0259] 13 C NMR (151 MHz, CDC13) δ 192.90, 171.23, 161.86, 149.11, 149.08, 140.16, 138.22, 132.82, 131.23, 129.55, 129.21, 129.12, 128.52, 128.50, 128.21, 121.09, 111.69, 111.03, 66.76, 55.96, 55.93, 34.47.

[0260] HRMS (ESI) m / z [M + H] + calcd for C 25 H 21 O5: 417.1697, not found.

[0261] Analytical data for a, b-unsaturated aldehyde 39

[0262] 1H NMR (600 MHz, CDC13) δ 9.63 (s, 1H), 7.44 - 7.34 (m, 6H), 7.23 (t, J = 7.0 Hz, 4H), 7.15 (t, J = 7.5 Hz, 1H), 7.01 (d, J = 7.6 Hz, 1H), 6.94 - 6.88 (m, 2H), 3.81 (s, 2H), 3.50 (s, 2H), 2.53 (s, 2H), 2.31 (s, 3H), 0.91 (s, 6H).

[0263] 13 C NMR (151 MHz, CDC13) δ 192.95, 171.21, 161.52, 140.23, 138.29, 138.01, 137.41, 132.96, 131.34, 131.19, 129.51, 129.24, 129.16, 128.57, 128.26, 127.80, 127.60, 126.86, 72.04, 44.91, 35.03, 34.50, 29.71, 24.38, 21.43.

[0264] HRMS (ESI) m / z [M + H] + calcd for C 29 H 31 O3: 427.2268, found: 427.2271.

[0265] Analytical data for a, b-unsaturated aldehyde 40

[0266] 1 H NMR (600 MHz, CDC13) δ 9.61 (s, 1H), 7.47 - 7.34 (m, 6H), 7.29 (t, J = 7.6 Hz, 2H), 7.22 (dq, J = 22.7, 5.4, 4.2 Hz, 7H), 4.14 (t, J = 6.5 Hz, 2H), 3.46 (s, 2H), 2.70 (t, J = 7.7 Hz, 2H), 2.01 - 1.91 (m, 2H).

[0267] 13 C NMR (151 MHz, CDC13) δ 192.97, 171.35, 161.73, 141.25, 140.24, 138.28, 132.96, 131.24, 129.53, 129.23, 129.15, 128.55, 128.46, 128.42, 128.23, 126.02, 64.24, 34.44, 32.13, 30.27.

[0268] HRMS (ESI) m / z [M + H]+ C 26 H 25 O3: 385.1798, found: 385.3801.

[0269] Analytical data for α,β-unsaturated aldehyde 41

[0270] 1 H NMR (600 MHz, CDC13) δ 9.58 (s, 1H), 7.45 - 7.27 (m, 9H), 7.21 (dd, J = 7.4, 2.8 Hz, 4H), 6.97 (t, J = 7.4 Hz, 1H), 6.93 (d, J = 8.1 Hz, 2H), 4.46 (t J = 4.8 Hz, 2H), 4.20 - 4.14 (m, 2H), 3.48 (s, 2H).

[0271] 13 C NMR (151 MHz, CDC13) δ 192.82, 171.15, 161.91, 158.56, 140.19, 138.25, 132.78, 131.20, 129.54, 129.51, 129.21, 129.07, 128.56, 128.21, 121.19, 114.72, 65.86, 63.19, 34.29.

[0272] HRMS (ESI) m / z [M + H] calcd for C + C 25 H 23 O4: 387.1591, not found.

[0273] Analytical data for α,β-unsaturated aldehyde 42

[0274] 1 H NMR (600 MHz, CDC13) δ 9.56 (s, 1H), 7.44 - 7.30 (m, 6H), 7.24 - 7.17 (m, 4H), 5.54 (d, J = 5.0 Hz, 1H), 4.61 (dd, J = 7.8, 2.5 Hz, 1H), 4.36 - 4.27 (m, 2H), 4.22 (dt, J = 10.9, 5.3 Hz, 2H), 4.04 (t, J = 6.3 Hz, 1H), 3.45 (s, 2H), 1.49 (s, 3H), 1.45 (s, 3H), 1.33 (d, J = 2.9 Hz, 6H).

[0275] 13C NMR (151 MHz, CDCI3) δ 192.89, 171.11, 161.74, 140.17, 138.30, 132.76, 131.27, 129.47, 129.18, 128.55, 128.15, 109.60, 108.78, 96.32, 71.04, 70.73, 70.49, 65.91, 63.86, 34.40, 26.05, 25.98, 25.02, 24.48.

[0276] HRMS (ESI) m / z [M + H] + calcd for C 29 H 33 O8: 509.2170, found: 509.2172.

[0277] Analytical data of a, b-unsaturated aldehyde 43

[0278] 1 H NMR (600 MHz, CDCI3) δ 9.57 (s, 1H), 7.45 - 7.30 (m, 6H), 7.20 (ddd, J = 7.2, 4.1, 2.1 Hz, 4H), 4.60 (dd, J = 7.9, 2.6 Hz, 1H), 4.41 (d, J = 11.7 Hz, 1H), 4.30 (d, J = 2.7 Hz, 1H), 4.25 - 4.19 (m, 1H), 4.12 (d, J = 12.1 Hz, 1H), 3.90 (dd, J = 12.9, 2.1 Hz, 1H), 3.75 (d, J = 12.9 Hz, 1H), 3.47 (q, J = 16.9 Hz, 2H), 1.52 (s, 3H), 1.46 (s, 3H), 1.33 (s, 6H).

[0279] 13 C NMR (151 MHz, CDCI3) δ 192.77, 170.73, 162.09, 140.14, 138.18, 132.49, 131.22, 129.56, 129.24, 129.14, 128.57, 128.20, 109.16, 108.77, 101.53, 70.82, 70.44, 70.12, 65.31, 61.28, 34.22, 26.50, 25.90, 25.23, 24.10.

[0280] HRMS (ESI) m / z [M + H] + calcd for C 29 H 33 O8: 509.2170, found: 509.2170.

[0281] Analytical data of α,β-unsaturated aldehyde 44

[0282] 1 H NMR (600 MHz, CDC13) δ 9.57 (s, 1H), 7.46 - 7.31 (m, 6H), 7.20 (dd, J = 7.0, 4.5 Hz, 4H), 4.63 (d, J = 9.7 Hz, 1H), 4.15 (d, J = 4.9 Hz, 2H), 3.63 (dd, J = 10.6, 5.7 Hz, 1H), 3.42 (s, 2H), 1.78 (d, J = 6.9 Hz, 1H), 1.42 (s, 9H), 0.94 (dd, J = 9.7, 6.8 Hz, 6H).

[0283] 13 C NMR (151 MHz, CDC13) δ 192.93, 171.25, 161.95, 155.72, 140.13, 138.19, 132.72, 131.21, 129.55, 129.27, 129.13, 128.58, 128.23, 65.07, 54.71, 34.33, 29.67, 28.37, 19.39, 18.48.

[0284] HRMS (ESI) m / z [M + H] + calcd for C 27 H 34 NO5: 452.2432, found: 452.2431.

[0285] Analytical data of α,β-unsaturated aldehyde 45

[0286] 1 H NMR (600 MHz, CDC13) δ 9.57 (s, 1H), 7.46 - 7.31 (m, 6H), 7.20 (dd, J = 7.0, 4.5 Hz, 4H), 4.63 (d, J = 9.7 Hz, 1H), 4.15 (d, J = 4.9 Hz, 2H), 3.63 (dd, J = 10.6, 5.7 Hz, 1H), 3.42 (s, 2H), 1.78 (d, J = 6.9 Hz, 1H), 1.42 (s, 9H), 0.94 (dd, J = 9.7, 6.8 Hz, 6H).

[0287] 13C NMR (151 MHz, CDCI3) δ 192.94, 171.24, 162.02, 155.18, 140.13, 138.18, 132.71, 131.21, 129.57, 129.28, 129.12, 128.59, 128.23, 67.51, 60.38, 45.57, 34.29, 28.39, 17.70.

[0288] HRMS (ESI) m / z [M+H] + calcd for C 25 H 30 NO5: 424.2119, found: 424.2120.

[0289] Analytical data of a, b-unsaturated aldehyde 46

[0290] 1 H NMR (600 MHz, CDCI3) δ 9.52 (s, 1 H), 7.41 - 7.28 (m, 6 H), 7.19 - 7.12 (m, 4 H), 5.36 (d, J = 8.0 Hz, 1 H), 4.53 - 4.42 (m, 1 H), 4.13 (t, J = 6.2 Hz, 2 H), 3.71 (s, 3 H), 3.37 (s, 2 H), 2.92 (dt, J = 14.6, 7.2 Hz, 2 H), 2.55 (t, J = 7.2 Hz, 2 H), 1.85 (t, J = 6.8 Hz, 2 H), 1.39 (s, 9 H).

[0291] 13 C NMR (151 MHz, CDCI3) δ 192.92, 192.90, 171.52, 171.25, 161.89, 155.17, 140.17, 138.21, 132.81, 131.21, 129.54, 129.25, 129.11, 128.54, 128.22, 63.19, 53.35, 52.52, 34.54, 34.34, 29.09, 28.62, 28.30.

[0292] HRMS (ESI) m / z [M+H] + calcd for C 29 H 36 NO7S: 542.2207, found: 542.2207.

[0293] The above embodiments describe the technical solutions and advantages of the present application in detail. It should be understood that the above description is only a specific embodiment of the present application and is not intended to limit the present application. Any modification, supplement, and equivalent replacement within the principle range of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing α,β-unsaturated aldehydes based on the synergistic catalytic reaction of nickel and visible light to propargyl ether rearrangement, the reaction process of which is shown below: ； Compound 1 is selected from: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ； Compound 2 is selected from: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ； The photocatalyst is selected from: 、 、 、 、 or ; The nickel catalyst is selected from: Nickel chloride, nickel acetylacetone, nickel bromide, nickel bromide with ethylene glycol dimethyl ether, or nickel acetate; The ligands are selected from: 、 、 、 、 、 , or ; The alkali is selected from: Sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, potassium phosphate, or dipotassium hydrogen phosphate.

2. The preparation method according to claim 1, characterized in that, The wavelength of the blue light is 390~440 nm.

3. The preparation method according to claim 1, characterized in that, The organic solvents mentioned are selected from: Acetonitrile, acetone, toluene, ethyl acetate, tetrahydrofuran, ethylene glycol dimethyl ether, 1,2-dichloroethane, 1,4-dioxane, or dimethyl sulfoxide.

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