Method for preparing alpha, beta-unsaturated aldehyde based on nickel and visible light concerted catalysis of propargyl ether rearrangement reaction

Abstract

The invention discloses a method for preparing alpha, beta-unsaturated aldehyde based on nickel and visible light synergistic catalysis of propargyl ether rearrangement reaction, which comprises the following step: in the presence of a nickel catalyst, a ligand, a photocatalyst and alkali and under the condition of blue light irradiation, reacting propargyl ether of a formula (1) with a bromide of a formula (2) in an organic solvent to generate an alpha, beta-unsaturated aldehyde compound of a formula (3). The preparation method provided by the invention has the advantages of cheap and easily available reaction raw materials, simple reaction operation, wide application range of reaction substrates, easy amplification of reaction, mild reaction conditions and the like, and can realize industrial production and application. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for preparing α, β-unsaturated aldehyde based on a propargyl ether rearrangement reaction catalyzed by nickel and visible light. Background Art

[0002] In organic synthesis, α,β-unsaturated aldehydes are a very important class of synthons. For example, α,β-unsaturated acids can be obtained through oxidation reactions; saturated alkyl aldehydes and allyl alcohols can be obtained through reduction reactions; epoxides can be obtained through epoxidation reactions; and chroman compounds can be obtained through cyclization reactions. At the same time, α,β-unsaturated aldehydes also have good pharmacological activities, such as anti-tumor activity, anti-inflammatory activity, antifungal and antibacterial activity, etc.

[0003] The 1,4-aryl migration rearrangement reaction of propargyl ether is a very efficient and simple method to obtain α,β-unsaturated aldehyde compounds. In 2017, Liu's research group reported a method for synthesizing α,β-unsaturated aldehyde compounds based on the 1,4-aryl migration strategy (C.-H. Guo, D.-Q. Chen, S. Chen, X.-Y. Liu, Adv. Synth. Catal. 2017, 359, 2901-2906.), and disclosed a method using AgSCF 3 As a free radical precursor, K 2 S 2 O 8 As an oxidant, the propargyl ether 1,4-aryl migration rearrangement reaction is achieved, and the reaction process is shown in the following equation:

[0004]

[0005] However, this technology has obvious defects: first, the reaction can only use AgSCF 3 As a free radical precursor, only SCF can be obtained 3 α,β-unsaturated aldehyde; secondly, the reaction requires excess K 2 S 2 O 8 As an oxidant, the reaction is not redox neutral and the atom economy of the reaction is relatively poor; thirdly, the reaction is not a catalytic method. Summary of the invention

[0006] The present invention provides a method for preparing an α,β-unsaturated aldehyde compound. The present invention uses simple and readily available propargyl ether and bromide as reaction substrates for the first time, and realizes the synthesis of multiple types of α,β-unsaturated aldehyde compounds by synergistic catalysis of nickel and visible light.

[0007] The technical solution of the present invention is as follows:

[0008] A method for preparing an α, β-unsaturated aldehyde based on a propargyl ether rearrangement reaction catalyzed by nickel and visible light, comprising: in the presence of a nickel catalyst, a ligand, a photocatalyst, a base and under blue light irradiation, in an organic solvent, reacting a compound of formula (1) with a compound of formula (2) 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] NiCl 2 、Ni(acac) 2 、NiBr 2 , Ethylene glycol dimethyl ether nickel bromide (NiBr 2 -glyme)、Ni(OAc 2 .

[0020] Preferably, the ligand is selected from:

[0021]

[0022] Preferably, the base is selected from:

[0023] Sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), cesium carbonate (Cs 2 CO 3 ), sodium bicarbonate (NaHCO 3 ), potassium bicarbonate (KHCO 3 ), potassium phosphate (K 3 PO 4 ), potassium dihydrogen phosphate (K 2 HPO4 ).

[0024] Preferably, the wavelength of the blue light is 390-440 nm; more preferably 390 nm, 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, and dimethyl sulfoxide.

[0026] Preferably, the molar ratio of the compound of formula (1), the compound of formula (2), the nickel catalyst, and 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 to 30°C.

[0028] The α,β-unsaturated aldehyde compounds prepared by the present invention are a very important class of organic synthesis intermediates and can be converted into a variety of organic compounds through various chemical reactions.

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

[0030] (1) The present invention is the first to use easily available propargyl ethers and bromides as reaction substrates, and to use nickel and visible light synergistic catalysis to achieve the synthesis of multiple types of α,β-unsaturated aldehyde compounds.

[0031] (2) The preparation method provided by the present invention can be applied to brominated esters, brominated amides, brominated thioesters, brominated esters derived from drug molecules, and brominated esters derived from sugar molecules, and has the advantages of simple and easy-to-obtain substrates and wide applicability.

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

[0033] The present invention will be further described in detail below in conjunction with the examples. It should be pointed out that the examples described below are intended to facilitate the understanding of the present invention and do not have any limiting effect on the present invention.

[0034] The operation methods in the following examples without specifying specific conditions are usually carried out under conventional conditions or under conditions recommended by the manufacturer. Unless otherwise specified, the mol% amounts of nickel catalyst and photocatalyst in each example are 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: Effects of PC1 and L1 on the reaction

[0040]

[0041] In a glove box, NiBr 2 -glyme(10mol%), L1(12mol%), PC1(3mol%), KHCO 3 (0.2mmol), propargyl ether 1 (0.1mmol) were weighed into a 4mL sample bottle, and solvent MeCN (1.0mL) and ethyl bromoacetate 2 (0.2mmol) were added in sequence, and the PTFE lid was screwed tight. The sample bottle was taken out of the glove box, placed under 440nm blue light, and reacted at 25°C for 12 hours. After the reaction was completed, the solvent was removed by rotary evaporation to obtain a crude product. The conversion rate and yield of the reaction were analyzed by thin layer chromatography or nuclear magnetic resonance, and the experimental results obtained were: the nuclear magnetic yield was 52%.

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

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

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

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

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

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

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

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

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

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

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

[0053] The only difference from Example 1 is that L1 is replaced by an equimolar amount of L2, and the rest is the same. The experimental results obtained are: the NMR yield is 30%.

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

[0055] The only difference from Example 1 is that L1 is replaced by an equimolar amount of L3, and the rest is the same. The experimental results obtained are: the NMR yield is 29%.

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

[0057] The only difference from Example 1 is that L1 is replaced by an equimolar amount of L4, and the rest is the same. The experimental results obtained are: the NMR yield is 45%.

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

[0059] The only difference from Example 1 is that L1 is replaced by an equimolar amount of L5, and the rest is the same. The experimental results obtained are: the NMR yield is 30%.

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

[0061] The only difference from Example 1 is that L6 is used in an equimolar amount to replace L1, and the rest is the same. The experimental results obtained are: the NMR yield is 35%.

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

[0063] The only difference from Example 1 is that L1 is replaced by an equimolar amount of L7, and the rest is the same. The experimental results obtained are: the NMR yield is 10%.

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

[0065] The only difference from Example 1 is that L1 is replaced by an equimolar amount of L8, and the rest is the same. The experimental results obtained are: the NMR yield is 15%.

[0066] Example 14: NiCl 2 Impact on reaction

[0067] The difference from Example 1 is that an equimolar amount of NiCl 2 Replacement of NiBr 2 -glyme, and the rest were the same. The experimental results showed that the NMR yield was 46%.

[0068] Example 15: Ni(acac) 2 Impact on reaction

[0069] The only difference from Example 1 is that an equimolar amount of Ni(acac) is used. 2 Replacement of NiBr 2 -glyme, and the rest were the same. The experimental results showed that the NMR yield was 37%.

[0070] Example 16: NiBr 2 Impact on reaction

[0071] The only difference from Example 1 is that an equimolar amount of NiBr 2 Replacement of NiBr 2 -glyme, and the rest were the same. The experimental results showed that the NMR yield was 50%.

[0072] Example 17: Ni(OAc) 2 Impact on reaction

[0073] The only difference from Example 1 is that an equimolar amount of Ni(OAc) is used. 2 Replacement of NiBr 2 -glyme, and the rest were the same. The experimental results showed that the NMR yield was 12%.

[0074] Example 18: Na 2 CO 3 Impact on reaction

[0075] The only difference from Example 1 is that an equivalent amount of Na 2 CO 3 Alternative KHCO 3 , the rest are the same, and the experimental results obtained are: the NMR yield is 28%.

[0076] Example 19: K 2 CO 3 Impact on reaction

[0077] The only difference from Example 1 is that an equivalent amount of K 2 CO 3 Alternative KHCO 3 , the rest are the same, the experimental results obtained are: the NMR yield is 25%.

[0078] Example 20: Cs 2 CO 3 Impact on reaction

[0079] The only difference from Example 1 is that an equivalent amount of Cs 2 CO 3Alternative KHCO 3 , the rest were the same, and the experimental results obtained were: the NMR yield was 40%.

[0080] Example 21: NaHCO 3 Impact on reaction

[0081] The difference from Example 1 is that an equivalent amount of NaHCO 3 Alternative KHCO 3 , the rest were the same, and the experimental results obtained were: the NMR yield was 39%.

[0082] Example 22: K 3 PO 4 Impact on reaction

[0083] The only difference from Example 1 is that an equivalent amount of K 3 PO 4 Alternative KHCO 3 , the rest were the same, and the experimental results obtained were: the NMR yield was 31%.

[0084] Example 23: K 2 HPO 4 Impact on reaction

[0085] The only difference from Example 1 is that an equivalent amount of K 2 HPO 4 Alternative KHCO 3 , the rest are the same, the experimental results obtained are: the NMR yield is 5%.

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

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

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

[0089] The only difference from Example 1 is that the wavelength of the blue light is 390 nm, and the rest are the same. The experimental results obtained are: the nuclear magnetic yield is 22%.

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

[0091] The only difference from Example 1 is that the solvent MeCN is replaced by an equal volume of EA, and the rest is the same. The experimental results obtained are: the NMR yield is 15%.

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

[0093] The only difference from Example 1 is that the solvent MeCN is replaced by an equal volume of DMSO, and the rest is the same. The experimental results obtained are: the NMR yield is 26%.

[0094] Example 28: Effect of Acetone Solvent on Reaction

[0095] The only difference from Example 1 is that the solvent MeCN is replaced by an equal volume of Acetone, and the rest is the same. The experimental results obtained are: the nuclear magnetic resonance yield is 22%.

[0096] Example 29: Effect of Toluene Solvent on Reaction

[0097] The only difference from Example 1 is that the solvent MeCN is replaced by an equal volume of toluene, and the rest is the same. The experimental results obtained are: the NMR yield is 6%.

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

[0099] The only difference from Example 1 is that the solvent MeCN is replaced by an equal volume of THF, and the rest is the same. The experimental results obtained are: the NMR yield is 18%.

[0100] Example 31: Effect of Ethylene Glycol Dimethyl Ether Solvent on Reaction

[0101] The only difference from Example 1 is that the solvent MeCN is replaced by an equal volume of ethylene glycol dimethyl ether, and the rest is the same. The experimental results obtained are: the nuclear magnetic yield is 8%.

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

[0103] The only difference from Example 1 is that the solvent MeCN is replaced by an equal volume of 1,2-dichloroethane, and the rest is the same. The experimental results obtained are: the NMR yield is 9%.

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

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

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

[0107]

[0108] In a glove box, NiBr 2 -glyme(10mol%), L1(12mol%), PC1(3mol%), KHCO 3(0.4mmol), propargyl ether (0.2mmol) were weighed into a 4mL sample bottle, and solvent MeCN (2.0mL) and bromide (0.4mmol) were added in sequence, and the PTFE lid was screwed tight. The sample bottle was taken out of the glove box, placed under 440nm blue light, and reacted at 25℃ for 12 hours. After the reaction was completed, the solvent was removed by rotary evaporator to obtain a crude product. The conversion rate and separation yield of the reaction were analyzed by thin layer chromatography or nuclear magnetic resonance, and the experimental results are shown in Table 1.

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

[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 (600MHz, Chloroform-d) δ9.58 (s, 1H), 7.44-7.34 (m, 7H), 7.21 (dt, J=6.4, 1.8Hz, 5H), 4.15 (q, J=7.1Hz, 2H), 3.41 (s, 2H), 1.25 (t, J=7.1Hz, 3H).

[0120] 13 C NMR (151 MHz, CDCl 3 )δ192.99, 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] + Calculate for C 19 H 19 O3 :295.1329, found:295.1330

[0122] Analytical data of α,β-unsaturated aldehyde 5

[0123] 1 Hc NMR (600 MHz, CDCl 3 )δ9.66(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=7.2Hz, 3.94H), 3.48 (s, 2H), 3.43 (s, 1.68H), 1.26 (dt, J=7.2, 3.6Hz, 5.83H).

[0124] 13 C NMR (151 MHz, CDCl 3 )δ192.94, 192.89, 171.40, 171.35, 161.41, 161.33, 142.44, 142.08, 14 0.25, 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] + Calculate for C 25 H 23 O 3 :371.1642, found:371.1641.

[0126] Analytical data of α,β-unsaturated aldehyde 6

[0127] 1 H NMR (600 MHz, CDCl 3)δ9.58 (s, 0.82H), 9.54 (s, 0.94H), 7.37 (t, J=3.2Hz, 5.62H), 7.21 (dt, J=8.6, 2.0Hz, 7.48H), 7.12 (dd, J=8.2, 3.7Hz, 3.9 1H), 4.19-4.12(m, 3.76H), 3.44(s, 2H), 3.39(s, 1.76H), 2.93(dp, J=9.3, 6.9Hz, 1.96H), 1.26(dd, J=7.0, 3.6Hz, 17.33H).

[0128] 13 C NMR (151 MHz, CDCl 3 )δ193.14, 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] + Calculate for C 22 H 25 O 3 :337.1798, found:337.1796.

[0130] Analytical data of α,β-unsaturated aldehyde 7

[0131] 1 H NMR (600 MHz, CDCl 3 )δ9.51 (s, 0.83H), 9.46 (s, 0.89H), 7.36-7.25 (m, 9.09H), 7.14 (dq, J=7.1, 1.8Hz, 3.69H), 7.08-7.01 (m, 3.70H) , 4.07 (dd, J=9.6, 7.1Hz, 3.74H), 3.37 (s, 2H), 3.32 (s, 1.75H), 1.25 (d, J=4.3Hz, 16.9H), 1.19-1.17 (m, 5.66H).

[0132] 13 C NMR (151 MHz, CDCl 3)δ193.14, 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] + Calculate for C 23 H 27 O 3 :351.1955, found:351.1954.

[0134] Analytical data of α,β-unsaturated aldehyde 8

[0135] 1 H NMR (600 MHz, CDCl 3 )δ9.55(d, J=13.2Hz, 1H), 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=1.9Hz, 2H), 1.26 (td, J=7.1, 5.5Hz, 3H).

[0136] 13 C NMR (151 MHz, CDCl 3 )δ192.87, 192.63, 171.36, 171.32, 164.38, 164.02, 162.72, 162.36, 16 0.66, 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, CDCl 3)δ-75.99, -110.94, -111.33, -111.35.

[0138] HRMS (ESI) m / z [M+H] + Calculate for C 19 H 18 FO 3 :313.1235, found:313.1234.

[0139] Analytical data of α,β-unsaturated aldehyde 9

[0140] 1 H NMR (600 MHz, CDCl 3 )δ9.57(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, 4.7Hz, 3.81H), 3.40 (s, 2H), 3.39 (s, 1.95H), 1.25 (td, J=7.1, 5.5Hz, 6.58H).

[0141] 13 C NMR (151 MHz, CDCl 3 )δ192.67, 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] + Calculate for C 19 H 18 C1O 3 :329.0939, found:329.0935.

[0143] Analytical data of α,β-unsaturated aldehyde 10

[0144] 1 H NMR (600 MHz, CDCl 3)δ9.58 (s, 0.51H), 9.50 (s, 0.96H), 7.44-7.33 (m, 4.49H), 7.20 (dt, J=6.9, 2.4Hz, 3.16H), 7.16-7.09 (m, 3.28H), 6.87 (dd, J=8.8, 2.0Hz, 3.21H), 4.15 (dq, J=14.1, 7.1Hz, 3.65H), 4.06 (p, J=7.0Hz, 3.77H), 3.46 (s, 2H), 3.38 (s , 1.18H), 1.43 (td, J=7.0, 5.3Hz, 5.38H), 1.26 (dt, J=10.3, 7.2Hz, 7.34H).

[0145] 13 C NMR (151 MHz, CDCl 3 )δ193.11, 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, 13 1.47, 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] + Calculate for C 21 H 23 O 4 :339.1591, found:339.1589.

[0147] Analytical data of α,β-unsaturated aldehyde 11

[0148] 1 H NMR (600 MHz, CDCl 3 )δ9.60 (s, 0.98H), 9.55 (s, 0.90H), 7.65 (dd, J=8.3, 2.9Hz, 3.98H), 7.47-7.32 (m, 10.07H), 7.24-7.1 6 (m, 4.03H), 4.15 (qd, J=7.1, 2.8Hz, 4.18H), 3.43 (s, 2H), 3.37 (s, 2.11H), 1.26 (t, J=7.1Hz, 6.89H).

[0149] 13 C NMR (151 MHz, CDCl3 )δ192.48, 192.13, 171.02, 159.73, 143.70, 141.87, 139.48, 137.38, 134.06, 133.75, 131.22 (p, J=33Hz), 131.30, 131.09, 129.8 3, 129.51, 129.41, 128.96, 128.75, 128.46, 125.59, 125.56, 125.27, 123.84 (q, J=272.5Hz), 61.09, 61.03, 34.29, 34.24, 14.12.

[0150] 19 F NMR (565 MHz, CDCl 3 )δ-62.80.

[0151] HRMS (ESI) m / z [M+H] + Calculate for C 20 H 17 F 3 O3: 363.1203, found: 363.1207.

[0152] Analytical data of α,β-unsaturated aldehyde 12

[0153] 1 H NMR (600 MHz, CDCl 3 )δ9.49 (s, 1H), 7.38-7.28 (m, 3H), 7.22-7.08 (m, 6H), 4.08 (qd, J=7.1, 3.5Hz, 2H), 3.33 (d, J=7.3Hz, 2H), 1.18 (td, J=7.2, 3.9Hz, 3H).

[0154] 13 C NMR (151 MHz, CDCl 3 )δ192.61, 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=257.7Hz), 61.03, 60.96, 34.41, 34.35, 14.10.

[0155] 19F NMR (565 MHz, CDCl 3 )δ-57.71.

[0156] HRMS (ESI) m / z [M+H] + Calculate for C 20 H 18 F 3 O 4 :379.1152, found:379.1148.

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

[0158] 1 H NMR (600 MHz, CDCl 3 )δ9.60 (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, 3.3Hz, 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, 2.4Hz, 6.65H).

[0159] 13 C NMR (151 MHz, CDCl 3 )δ192.88, 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] + Calculate for C 20 H 21 O 3 S: 341.1206, found: 341.1211.

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

[0162] 1H NMR (600 MHz, CDCl 3 )δ9.59 (s, 1.62H), 9.54 (s, 0.85H), 7.69 (dd, J=8.2, 3.6Hz, 5.98H), 7.49-7.33 (m, 15.16H), 7.22-7.1 3 (m, 5.56H), 4.15 (q, J=7.1Hz, 5.95H), 3.42 (s, 2H), 3.34 (s, 3.76H), 1.26 (td, J=7.1, 2.7Hz, 8.64H).

[0163] 13 C NMR (151 MHz, CDCl 3 )δ192.29, 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] + Calculate for C 20 H 17 NO 3 : 371.1642, not found.

[0165] Analytical data of α,β-unsaturated aldehyde 15

[0166] 1 H NMR (600 MHz, CDCl 3 )δ9.57(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=7.2Hz, 4H), 3.43 (s, 2H), 3.39 (s, 2H), 2.18 (d, J=2.7Hz, 6H), 1.25 (q, J=7.0Hz, 10H).

[0167] 13 C NMR (151 MHz, CDCl 3)δ192.05, 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] + Calculate for C 21 H 22 NO 4 :352.1543, found:342.1540.

[0169] Analytical data of α,β-unsaturated aldehyde 16

[0170] 1 H NMR (600 MHz, CDCl 3 )δ9.59(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, 7.1Hz, 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, 7.2Hz, 5.71H).

[0171] 13 C NMR (151 MHz, CDCl 3 )δ192.53, 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, 13 1.05, 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] + Calculate for C 21 H 21 O5 :353.1384, found:353.1385.

[0173] Analytical data of α,β-unsaturated aldehyde 17

[0174] 1 H NMR (600 MHz, CDCl 3 )δ9.60 (s, 1H), 9.56 (s, 0H), 7.96 (d, J = 1.9Hz, 1H), 7.45-7.28 (m, 5H), 7.19 (td, J = 4.2, 2.4Hz, 2H), 4 .15(qd, J=7.1, 1.6Hz, 2H), 3.42(s, 1H), 3.37(s, 1H), 2.62(s, 2H), 2.61(s, 2H), 1.25(tJ=7.2Hz, 4H).

[0175] 13 C NMR (151 MHz, CDCl 3 )δ197.33, 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] + Calculate for C 21 H 21 O 4 :337.1435, found:337.1439.

[0177] Analytical data of α,β-unsaturated aldehyde 18

[0178] 1 H NMR (600 MHz, CDCl 3 )δ9.57 (s, 0.90H), 9.57 (s, 0.91H), 7.46-7.29 (m, 9.99H), 7.16 (ddt, J=44.6, 7.5, 1.7Hz, 7 .85H), 4.15 (qd, J=7.1, 5.4Hz, 4.03H), 3.40 (s, 2H), 3.38 (s, 1.98H), 1.26 (qd, J=7.0Hz, 7H).

[0179] 13 C NMR (151 MHz, CDCl 3 )δ192.61, 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] + Calculate for C 19 H 18 C1O 3 :329.0939, found:329.0935.

[0181] Analytical data of α,β-unsaturated aldehyde 19

[0182] 1 H NMR (600 MHz, CDCl 3 )δ9.59(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=7.2Hz, 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, CDCl 3)δ192.96, 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] + Calculate for C 20 H 21 O 4 :325.1435, found:325.1430.

[0185] Analytical data of α,β-unsaturated aldehyde 20

[0186] 1 H NMR (600 MHz, CDCl 3 )δ9.51 (s, 0.85H), 7.40 (dt, J=30.4, 7.4Hz, 2.83H), 7.22 (d, J=7.2Hz, 1.97H), 6.86-6.82 (m, 1.92H), 6.74 (dd, J=8 .4, 2.0Hz, 0.92H), 4.16 (q, J=7.1Hz, 2H), 3.90 (s, 3H), 3.78 (s, 2.99H), 3.47 (s, 1.96H), 1.27 (t, J=7.2Hz, 4.32H).

[0187] 13 C NMR (151 MHz, CDCl 3 )δ193.04, 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] + Calculate for C 21 H 23 O 5 :355.1540, found:355.1537.

[0189] Analytical data of α,β-unsaturated aldehyde 21

[0190] 1 H NMR (600 MHz, CDCl 3 )δ9.61 (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, 2.7Hz, 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, 7.1Hz, 5.59H).

[0191] 13 C NMR (151 MHz, CDCl 3 )δ193.09, 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, 12 9.46, 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] + Calculate for C 21 H 21 O 5 :353.1384, found:353.1380.

[0193] Analytical data of α,β-unsaturated aldehyde 22

[0194] 1 H NMR (600 MHz, CDCl 3)δ9.64 (s, 0.83H), 9.62 (s, 0.90H), 7.95-7.70 (m, 7.74H), 7.54 (ddd, J=16.3, 8.2, 5.3Hz, 3.85H), 7.46-7.35 (m, 5.66H), 7.26 (td, J =4.4, 2.0Hz, 5.32H), 7.20 (dd, J=8.5, 1.8Hz, 0.99H), 4.17 (p, J=7.4Hz, 3.67H), 3.48 (s, 2H), 3.47 (s, 1.7H), 1.28-1.25 (m, 5.86H).

[0195] 13 C NMR (151 MHz, CDCl 3 )δ192.97, 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, 1 29.32, 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] + Calculate for C 23 H 21 O 3 :345.1485, found:345.1484.

[0197] Analytical data of α,β-unsaturated aldehyde 23

[0198] 1 H NMR (600 MHz, CDCl 3 )δ9.62 (d, J=9.6Hz, 1H), 7.95-7.78 (m, 2H), 7.63-7.54 (m, 2H), 7.52-7.2 0 (m, 9H), 4.18 (q, J=7.1Hz, 2H), 3.48 (d, J=2.8Hz, 2H), 1.29-1.25 (m, 4H).

[0199] 13 C NMR (151 MHz, CDCl 3)δ192.98, 171.52, 171.44, 161.91, 161.73, 156.83, 156.80, 156.72, 156.49, 14 0.53, 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] + Calculate for C 25 H 21 O 4 :385.1435, found:385.1431.

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

[0202] 1 H NMR (600 MHz, CDCl 3 )δ9.60(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, 2.9Hz, 1.99H), 6.99 (d, J=7.5Hz, 1.05H), 6.67-6.58 (m, 2.08H), 4.15 (qd, J=7.1, 4.2Hz, 2.01H), 3.98 (td, J=5.6, 2.3Hz, 2.09H), 3.42 (d, J=7.9Hz, 2H), 2.29 (s, 3.08H), 2. 16 (s, 3.09H), 1.93-1.83 (m, 4.26H), 1.38 (d, J=3.5Hz, 6.08H), 1.26 (q, J=6.9Hz, 3.85H).

[0203] 13 C NMR (151 MHz, CDCl 3)δ192.86, 192.67, 192.64, 176.12, 176.04, 171.32, 160.77, 160.63, 156.87, 152.09, 15 1.73, 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] + Calculate for C 32 H 35 O 5 :499.2479,found:499.2484.

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

[0206] 1 H NMR (600 MHz, CDCl 3 )δ9.57 (s, 0.88H), 9.54 (d, J=1.7Hz, 1.01H), 7.43-7.33 (m, 5.85H), 7.29 (dt, J=8.4, 2.1Hz, 3.85H), 7.2 2-7.12 (m, 11.58H), 7.03 (ddd, J=8.7, 4.3, 2.0Hz, 3.90H), 4.19-4.08 (m, 4.03H), 3.95 (dd, J=7.1, 3.8Hz, 2H), 3.40 (t, J=2.0Hz, 4H), 2.47 (s, 2.02H), 2.46 (s, 1.92H), 1.86 (hept, J=6.8Hz, 2.06H), 1.61 (d, J=2. 5Hz, 2.93H), 1.60 (d, J=2.6Hz, 2.74H), 1.25 (td, J=7.2, 3.4Hz, 6.19H), 0.90 (dd, J=6.7, 1.9Hz, 11.89H).

[0207] 13 C NMR (151 MHz, CDCl 3)δ192.85, 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, 133.24,1 33.14, 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] + Calculate for C 34 H 39 O 6 :543.2741, found:543.2739.

[0209] Analytical data of α,β-unsaturated aldehyde 26

[0210] 1 H NMR (600 MHz, CDCl 3 )δ9.57(s, 0.88H), 9.55(s, 1.02H), 7.45-7.33(m, 9.96H), 7.21-7.13(m, 7.84H), 4.1 5 (qd, J=7.1, 4.8Hz, 4.07H), 3.40 (s, 2H), 3.39 (s, 2.04H), 1.26 (q, J=6.7Hz, 6.32H).

[0211] 13 C NMR (151 MHz, CDCl 3 )δ192.69, 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] + Calculate for C 19H 18 C1O 3 :329.0939, found:329.0936.

[0213] Analytical data of α,β-unsaturated aldehyde 27

[0214] 1 H NMR (600 MHz, CDCl 3 )δ9.60 (s, 0H), 9.55 (s, 0H), 7.65 (dd, J=8.3, 2.8Hz, 2H), 7.47-7.31 (m, 6H), 7.20 (dd, J=6. 5, 2.2Hz, 2H), 4.15 (qd, J=7.1, 2.7Hz, 2H), 3.43 (s, 1H), 3.37 (s, 1H), 1.26 (tJ=7.1Hz, 4H).

[0215] 13 C NMR (151 MHz, CDCl 3 ) δ192.49, 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==33Hz), 131.09, 129. 84, 129.51, 129.41, 128.96, 128.75, 125.58 (q, J=3.6Hz), 125.26 (q, J=3.2Hz), 123.83 (q, J=270Hz), 61.10, 61.03, 34.29, 34.25, 14.12.

[0216] 19 F NMR (565 MHz, CDCl 3 )δ-62.80.

[0217] HRMS (ESI) m / z [M+H] + Calculate for C 20 H 18 F 3 O 3 :363.1203,found:363.1201.Analysis data of α,β-unsaturated aldehyde 28

[0218] 1 H NMR (600 MHz, CDCl 3)δ9.66(s, 0.83H), 9.59(s, 0.92H), 7.60(d, J=7.7Hz, 7.7H), 7.48-7.35(m, 11.29H), 7.31-7.24( m, 7.59H), 4.17 (p, J=7.3Hz, 3.89H), 3.48 (s, 2H), 3.43 (s, 1.8H), 1.27 (td, J=7.1, 2.9Hz, 6.17H).

[0219] 13 C NMR (151 MHz, CDCl 3 )δ192.96, 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] + Calculate for C 25 H 23 O 3 :371.1642, found:371.1641.

[0221] Analytical data of α,β-unsaturated aldehyde 29

[0222] 1 H NMR (600 MHz, CDCl 3 )δ9.58 (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=8.2Hz, 3.30H), 4.15 (dq, J =14.0, 7.1Hz, 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, 7.2Hz, 5.97H).

[0223] 13 C NMR (151 MHz, CDCl 3)δ193.07, 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] + Calculate for C 20 H 21 O 4 :325.1435, found:325.1434.

[0225] Analytical data of α,β-unsaturated aldehyde 30

[0226] 1 H NMR (600 MHz, CDCl 3 )δ9.63 (s, 1H), 7.49-7.31 (m, 8H), 7.29-7.20 (m, 5H), 7.08 (d, J=7.9Hz, 2H), 3.66 (s, 2H).

[0227] 13 C NMR (151 MHz, CDCl 3 )δ192.84, 169.99, 162.35, 150.89, 140.21, 138.15, 132.66, 131.23, 12 9.66, 129.38, 129.14, 128.67, 128.28, 125.83, 121.55, 115.34, 34.52.

[0228] HRMS (ESI) m / z [M+H] + Calculate for C 23 H 19 O 3 :343.1329, found:343.1332.

[0229] Analytical data of α,β-unsaturated aldehyde 31

[0230] 1 H NMR (600 MHz, CDCl 3)δ9.57 (s, 1H), 7.43-7.30 (m, 6H), 7.24-7.16 (m, 4H), 3.34 (s, 2H), 1.45 (d, J=1.3Hz, 9H).

[0231] 13 C NMR (151 MHz, CDCl 3 )δ192.99, 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] + Calculate for C 21 H 23 O 3 :323.1642, found:323.1646.

[0233] Analytical data of α,β-unsaturated aldehyde 32

[0234] 1 H NMR (600 MHz, CDCl 3 )δ9.54 (s, 1H), 7.44-7.31 (m, 8H), 7.19 (d, J = 7.5Hz, 2H), 6.00 (s, 1H), 3.30 (s, 2H), 2.79 (d, J = 4.8Hz, 3H).

[0235] 13 C NMR (151 MHz, CDCl 3 )δ194.19, 170.95, 162.74, 139.92, 138.57, 133.29, 131.24, 129.84, 129.39, 129.32, 128.30, 128.14, 36.19, 26.48.

[0236] HRMS (ESI) m / z [M+H] + Calculate for C 18 H 18 NO 2 :280.1332, found:280.1334.

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

[0238] 1 H NMR (600 MHz, CDCl 3)δ9.56 (d, J=1.8Hz, 1H), 7.41-7.32 (m, 6H), 7.28 (ddd, J=5.4, 4.0, 2.1Hz, 2H) , 7.21-7.17 (m, 2H), 3.42 (s, 2H), 3.00 (d, J = 1.9Hz, 3H), 2.97 (d, J = 1.9Hz, 3H).

[0239] 13 C NMR (151 MHz, CDCl 3 )δ193.52, 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] + Calculate for C 19 H 20 NO 2 :294.1489, found:294.1486.

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

[0242] 1 H NMR (600 MHz, CDCl 3 )δ9.59 (s, 1H), 7.39 (h, J=8.4, 7.9Hz, 6H), 7.30 (d, J=7.5Hz, 2H), 7.24-7.20 (m, 7H), 3.69 (s, 2H), 3.14 (t, J=7.8Hz, 2H), 2.87 (t, J=7.8Hz, 2H).

[0243] 13 C NMR (151 MHz, CDCl 3 )δ196.88, 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] + Calculate for C 25 H 23 O 2 S: 387.1414, not found.

[0245] Analytical data of α,β-unsaturated aldehyde 35

[0246] 1 H NMR (600 MHz, CDCl 3 )δ9.58 (s, 1H), 7.44-7.33 (m, 6H), 7.23-7.15 (m, 4H), 4.12 (t, J=6.5Hz, 2H), 3.41 (s, 2H), 3.39 (t, J=6.3Hz, 2H), 3.33 (s, 3H), 1.73-1.68 (m, 2H), 1.65-1.61 (m, 2H).

[0247] 13 C NMR (151 MHz, CDCl 3 )δ191.88, 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] + Calculate for C 22 H 25 O 4 :353.1748, found:353.1754.

[0249] Analytical data of α,β-unsaturated aldehyde 36

[0250] 1 H NMR (600 MHz, CDCl 3 )δ9.58 (s, 1H), 7.45-7.32 (m, 6H), 7.24-7.17 (m, 4H), 4.71 (td, J=10.9, 4.4Hz, 1H), 3. 47-3.35 (m, 2H), 2.03-1.96 (m, 1H), 1.89 (pd, J=7.0, 2.7Hz, 1H), 1.67 (ddt, J=16.8, 6.7 , 2.8Hz, 3H), 1.47 (ddt, J=12.0, 6.1, 2.8Hz, 1H), 1.38-1.34 (m, 1H), 1.06 (dd, J=12.8, 3.3Hz, 1H), 0.97 (q, J=11.8Hz, 1H), 0.90 (dd, J=6.9, 5.1Hz, 6H), 0.78 (d, J=7.0Hz, 3H).

[0251] 13 C NMR (151 MHz, CDCl 3 )δ192.83, 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] + Calculate for C 27 H 33 O 3 :405.2424, found:405.2426.

[0253] Analytical data of α,β-unsaturated aldehyde 37

[0254] 1 H NMR (600 MHz, CDCl 3 )δ9.58 (s, 1H), 7.37 (ddt, J=19.7, 14.5, 7.2Hz, 7H), 7.18 (dd, J=19.8, 7.2Hz, 4H), 6.91-6.75 (m, 3H), 5.96 (s, 2H), 5.04 (s, 2H), 3.46 (s, 2H).

[0255] 13 C NMR (151 MHz, CDCl 3 )δ192.88, 171.16, 161.88, 147.82, 147.62, 140.16, 138.22, 132.78, 131.24, 129.71, 1 29.54, 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] + Calculate for C 25 H 21 O 5 :401.1384, not found.

[0257] Analytical data of α,β-unsaturated aldehyde 38

[0258] 1 H NMR (600 MHz, CDCl 3)δ9.58 (s, 1H), 7.35 (ddt, J=29.1, 14.1, 7.1Hz, 6H), 7.23-7.11 (m, 4H), 6.95-6.80 (m, 3H), 5.08 (s, 2H), 3.89 (d, J=5.1Hz, 6H), 3.46 (s, 2H).

[0259] 13 C NMR (151 MHz, CDCl 3 )δ192.90, 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] + Calculate for C 25 H 21 O 5 :417.1697, not found.

[0261] Analytical data of α,β-unsaturated aldehyde 39

[0262] 1 H NMR (600 MHz, CDCl 3 )δ9.63 (s, 1H), 7.44-7.34 (m, 6H), 7.23 (t, J=7.0Hz, 4H), 7.15 (t, J=7.5Hz, 1H), 7.01 (d, J=7. 6Hz, 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, CDCl 3 )δ192.95, 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] + Calculate for C 29 H 31 O 3 :427.2268, found:427.2271.

[0265] Analytical data of α,β-unsaturated aldehyde 40

[0266] 1 H NMR (600 MHz, CDCl 3 )δ9.61 (s, 1H), 7.47-7.34 (m, 6H), 7.29 (t, J=7.6Hz, 2H), 7.22 (dq, J=22.7, 5.4, 4.2H z, 7H), 4.14 (t, J=6.5Hz, 2H), 3.46 (s, 2H), 2.70 (t, J=7.7Hz, 2H), 2.01-1.91 (m, 2H).

[0267] 13 C NMR (151 MHz, CDCl 3 )δ192.97, 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] + Calculate for C 26 H 25 O 3 :385.1798, found:385.3801.

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

[0270] 1 H NMR (600 MHz, CDCl 3 )δ9.58 (s, 1H), 7.45-7.27 (m, 9H), 7.21 (dd, J=7.4, 2.8Hz, 4H), 6.97 (t, J=7.4Hz, 1H), 6.93 (d, J=8.1Hz, 2H), 4.46 (tJ=4.8Hz, 2H), 4.20-4.14 (m, 2H), 3.48 (s, 2H).

[0271] 13 C NMR (151 MHz, CDCl3 )δ192.82, 171.15, 161.91, 158.56, 140.19, 138.25, 132.78, 131.20, 129.54, 1 29.51, 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] + Calculate for C 25 H 23 O 4 : 387.1591, not found.

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

[0274] 1 H NMR (600 MHz, CDCl 3 )δ9.56 (s, 1H), 7.44-7.30 (m, 6H), 7.24-7.17 (m, 4H), 5.54 (d, J = 5.0Hz, 1H), 4.61 (dd, J = 7.8, 2.5Hz, 1H), 4.36-4.27 (m, 2H), 4.22 (dt, J=10.9, 5.3Hz, 2H), 4.04 (t, J=6.3Hz, 1H), 3.45 (s, 2H), 1.49 (s, 3H), 1.45 (s, 3H), 1.33 (d, J=2.9Hz, 6H).

[0275] 13 C NMR (151 MHz, CDCl 3 )δ 192.89, 171.11, 161.74, 140.17, 138.30, 132.76, 131.27, 129.47, 129.18, 128.55, 128.15, 1 09.60, 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] + Calculate for C 29 H 33 O 8 :509.2170,found:509.2172.

[0277] Analytical data of α,β-unsaturated aldehyde 43

[0278] 1 H NMR (600 MHz, CDCl 3 )δ9.57 (s, 1H), 7.45-7.30 (m, 6H), 7.20 (ddd, J=7.2, 4.1, 2.1Hz, 4H), 4.60 ( dd, J=7.9, 2.6Hz, 1H), 4.41 (d, J=11.7Hz, 1H), 4.30 (d, J=2.7Hz, 1H), 4.25-4 .19 (m, 1H), 4.12 (d, J = 12.1Hz, 1H), 3.90 (dd, J = 12.9, 2.1Hz, 1H), 3.75 (d, J = 12.9Hz, 1H), 3.47(q, J=16.9Hz, 2H), 1.52(s, 3H), 1.46(s, 3H), 1.33(s, 6H).

[0279] 13 C NMR (151 MHz, CDCl 3 )δ192.77, 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] + Calculate for C 29 H 33 O 8 :509.2170,found:509.2170.

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

[0282] 1 H NMR (600 MHz, CDCl 3 )δ9.57 (s, 1H), 7.46-7.31 (m, 6H), 7.20 (dd, J=7.0, 4.5Hz, 4H), 4.63 (d, J=9.7Hz, 1H), 4.15 (d, J=4.9Hz, 2H) , 3.63 (dd, J=10.6, 5.7Hz, 1H), 3.42 (s, 2H), 1.78 (d, J=6.9Hz, 1H), 1.42 (s, 9H), 0.94 (dd, J=9.7, 6.8Hz, 6H).

[0283] 13 C NMR (151 MHz, CDCl 3 )δ192.93, 171.25, 161.95, 155.72, 140.13, 138.19, 132.72, 131.21, 129.55, 12 9.27, 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] + Calculate for C 27 H 34 NO 5 :452.2432, found:452.2431.

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

[0286] 1 H NMR (600 MHz, CDCl 3 )δ9.57 (s, 1H), 7.54-7.32 (m, 6H), 7.20 (d, J=7.0Hz, 4H), 4.66 (s, 1H), 4.08 (td, J =15.3, 8.7Hz, 2H), 3.93 (s, 1H), 3.44 (s, 2H), 1.42 (s, 9H), 1.15 (d, J = 6.8Hz, 3H).

[0287] 13 C NMR (151 MHz, CDCl 3 )δ192.94, 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] + Calculate for C 25 H 30 NO 5 :424.2119, found:424.2120.

[0289] Analytical data of α,β-unsaturated aldehyde 46

[0290] 1 H NMR (600 MHz, CDCl 3)δ9.52 (s, 1H), 7.41-7.28 (m, 6H), 7.19-7.12 (m, 4H), 5.36 (d, J = 8.0Hz, 1H), 4.53-4.42 (m, 1H), 4.13 (t, J = 6.2Hz, 2H ), 3.71 (s, 3H), 3.37 (s, 2H), 2.92 (dt, J = 14.6, 7.2Hz, 2H), 2.55 (t, J = 7.2Hz, 2H), 1.85 (t, J = 6.8Hz, 2H), 1.39 (s, 9H).

[0291] 13 C NMR (151 MHz, CDCl 3 )δ192.92, 192.90, 171.52, 171.25, 161.89, 155.17, 140.17, 138.21, 132.81, 131.21, 129.5 4, 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] + Calculate for C 29 H 36 NO7S: 542.2207, found: 542.2207.

[0293] The embodiments described above provide a detailed description of the technical solutions and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, supplements and equivalent substitutions made within the scope of the principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing α, β-unsaturated aldehydes based on nickel and visible light catalytic rearrangement of propargyl ether, characterized in that: include: In the presence of a nickel catalyst, a ligand, a photocatalyst, a base and under blue light irradiation, in an organic solvent, the compound of formula (1) reacts with the compound of formula (2) to generate an α,β-unsaturated aldehyde compound of formula (3):

2. The preparation method according to claim 1, characterized in that: The compound of formula (1) is selected from:

3. The preparation method according to claim 1, characterized in that: The compound of formula (2) is selected from:

4. The preparation method according to claim 1, characterized in that: The photocatalyst is selected from:

5. The preparation method according to claim 1, characterized in that: The nickel catalyst is selected from: Nickel chloride, nickel acetylacetonate, nickel bromide, ethylene glycol dimethyl ether nickel bromide or nickel acetate.

6. The preparation method according to claim 1, characterized in that: The ligand is selected from:

7. The preparation method according to claim 1, characterized in that: The base is selected from: Sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, potassium phosphate or dipotassium hydrogen phosphate.

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

9. The preparation method according to claim 1, characterized in that: The organic solvent is 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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