Method for preparing trans-olefin through semi-hydrogenation of allene under catalysis of chromium

Abstract

According to the method, an allene compound is adopted as a raw material, a cyclic (alkyl) (amino) carbene chromium complex of which the side arm is substituted by diphenylphosphine is adopted as a catalyst, hydrogen is adopted as a hydrogen source, and the trans-olefin is obtained through full reaction. The method is mild in preparation condition, low in cost, wide in raw material source, simple to operate and good in regioselectivity and stereoselectivity, and can be carried out without a guiding base.

Description

Technical Field

[0001] The invention relates to the technical field of olefin preparation, and in particular to a method for preparing trans-olefin by chromium-catalyzed allene semi-hydrogenation. Background Art

[0002] Allenes have unique physical and chemical properties because two carbon-carbon double bonds share one carbon atom. They are widely used in natural product synthesis, pharmaceutical chemistry, and material science. In view of their wide range of sources, their conversion has also received much attention. The method of preparing olefin compounds using allenes can be divided into two types: using hydrogen as the hydrogen source and using non-hydrogen as the hydrogen source, depending on the source of hydrogen.

[0003] Using non-hydrogen as the hydrogen source, equivalent sodium / liquid nitrogen, hydrazine and diisobutylaluminum hydride are usually used to achieve the semi-reduction reaction of some allenes, but this scheme has the disadvantages of narrow substrate range, poor functional group compatibility, low yield, harsh reaction conditions and poor selectivity, and the use of equivalent reducing agents has the disadvantages of high cost and poor atom economy. When water is used as the hydrogen source, heterogeneous palladium / carbon (Pd / C) catalysts can complete the selective semi-hydrogenation reaction of 1,1-disubstituted allenes under the mediation of boric acid, but there are disadvantages of low yield, narrow substrate range and poor stereoselectivity. When formic acid is used as the hydrogen source, palladium catalysts can achieve the regioselective semi-hydrogenation reaction of allenylamines under ligand regulation to obtain enamine and allylamine derivatives. When diethyl malonate is used as the hydrogen source, the semi-reduction reaction of amino allenyl phosphate is achieved by electrocatalytic reduction, but the reaction has the problem of poor stereoselectivity. When Hantzsch ester is used as hydrogen source, under the action of chiral phosphine ligand, rhodium-catalyzed 1,1-disubstituted allenes are highly regioselective and enantioselective semi-reduction reactions are achieved to obtain a series of allyl compounds with chiral structures.

[0004] Using hydrogen as the gas source and the non-metallic DABCO / B(C6F5)3 catalytic system, the semi-hydrogenation reaction of electron-deficient allenes can be achieved. The homogeneous catalyst tri(triphenylphosphine)rhodium chloride (RhCl(PPh3)3) can achieve the semi-hydrogenation reaction of some cyclic and non-cyclic allenes, and obtain cis-olefins in a regio- and stereo-selective manner. The diimine-coordinated palladium catalyst (Pd(Ar-BIAN)(alkene)) uses the phosphonate, sulfonate and carbonate groups on the allene as directing groups to achieve highly chemical, regio- and stereo-selective semi-hydrogenation reactions of allenes to synthesize the corresponding cis-olefins. The heterogeneous palladium / carbon (Pd / C) catalyst successfully achieved the semi-hydrogenation reaction of α-aminophosphoryl ester allenes, and obtained a series of cis-α-aminophosphoryl ester olefins with pharmaceutical activity. The noble metal rhodium catalyst combined with the chiral ligand, using the directing effect of the sulfonyl group, achieved a highly regioselective and enantioselective semi-hydrogenation reaction of tetrasubstituted allenyl sulfone compounds, and synthesized a series of chiral allyl sulfone compounds. Using the abundant transition metal nickel as a catalyst, the directing effect of the sulfonyl group was used to achieve the kinetic resolution of allenyl sulfone compounds, and the chiral trans-allyl sulfone compounds enriched in enantiomers were obtained with high regioselectivity, stereoselectivity and enantioselectivity.

[0005] The above-mentioned direct reduction with a metered non-hydrogen reducing agent and the semi-reduction reaction of allenes with a metered acid and an organic hydrogen source under transition metal catalysis can be achieved, but there are disadvantages such as low atom economy, environmentally unfriendly reaction, and unclean system. Using hydrogen as a hydrogen source and transition metal catalysis can achieve the selective semi-hydrogenation reaction of allenes economically and efficiently, but this type of reaction has high requirements on the substrate and is often targeted at specific substrates, such as requiring the allene substrate to have a directing group. Summary of the invention

[0006] The present invention aims at solving the problems in the prior art and provides a method for preparing trans-olefins by semi-hydrogenation of allenes catalyzed by chromium.

[0007] The technical solution adopted by the present invention is:

[0008] A method for preparing trans-olefins by chromium-catalyzed semi-hydrogenation of allenes,

[0009] The allene compound is used as a raw material, the side arm is a cyclic (alkyl) (amino) carbene chromium complex substituted with diphenylphosphine as a catalyst, and hydrogen is used as a hydrogen source to fully react to obtain a trans-olefin;

[0010] The catalyst structure is as follows:

[0011]

[0012] Further, the structure of the allene compound is as follows:

[0013]

[0014] Where: R 1 Selected from one of the following groups:

[0015] naphthyl, 4-methylphenyl, 4-ethylphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 4-benzyloxyphenyl, 4-(4-bromobenzyloxy)phenyl, 4-(3-chlorobenzyloxy)phenyl, 4-(4-fluorobenzyloxy)phenyl, 4-(3-nitrobenzyloxy)phenyl, 4-(nitrilemethoxy)phenyl, 4-(3-methylbut-2-en-1-yloxy)phenyl, 4-(pyridine-2-methoxy)phenyl, 4-methoxycarbonylmethoxyphenyl, 4-(tert-butyldimethylsilyloxy)phenyl, 4-(cyclopropanemethoxy)phenyl, 4-(phenoxy)phenyl, 4-biphenyl, 4-(4-tert-butylphenyl)benzene phenyl, 4-(4-(trifluoromethyl)phenyl)phenyl, 4-(4-(trifluoromethoxy)phenyl)phenyl, 4-(4-(trimethylsilyl)phenyl)phenyl, 4-(3-fluoro-4-methoxyphenyl)phenyl, 4-(2-methylthiophenyl)phenyl, 4-(furan-3-yl)phenyl, 4-(thiophen-3-yl)phenyl, 4-(1-H-pyrazol-1-yl)phenyl, 2,3-dihydrobenzofuran-6-yl, benzo[d][1,3]dioxolan-5-yl, 4-(benzo[d][1,3]dioxolan-5-yl)phenyl, 4-dimethylaminophenyl, 4-tert-butyloxycarbonylaminophenyl;

[0016] R 2 One selected from the following groups: hydrogen, methyl, ethyl, propyl, butyl;

[0017] R 3 One selected from the following groups: hydrogen, ethyl, butyl, benzyl, trimethylsilyl;

[0018] R 4 For hydrogen.

[0019] Furthermore, magnesium is used as a reducing agent in the reaction process, and an additive is also included.

[0020] Furthermore, the reaction temperature is 40-70° C., the hydrogen pressure is 1-4 MPa, and the reaction time is 12-24 h.

[0021] Furthermore, the amount of the catalyst used is 1% to 5% of the molar amount of the allene compound.

[0022] Furthermore, the additive is chlorosilane.

[0023] Furthermore, the chlorosilane is one of trimethylchlorosilane, triethylchlorosilane, dimethylchlorohydrosilane and diphenylchlorohydrosilane.

[0024] Furthermore, the molar ratio of magnesium to allene compound is 0.5 to 2:1.

[0025] Furthermore, the molar ratio of the chlorosilane to the allene compound is 0.5 to 2:1.

[0026] The beneficial effects of the present invention are:

[0027] The method of the invention has mild preparation conditions, low cost, wide sources of raw materials, simple operation, good regio- and stereo-selectivity, and can be carried out without a directing group. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is the reaction equation of the present invention.

[0029] Figure 2 It is the allene compound used in the embodiments of the present invention.

[0030] Figure 3 It is a schematic diagram of the preparation method of the allene compound in the present invention. DETAILED DESCRIPTION

[0031] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

[0032] like Figure 1 As shown, a method for preparing trans-olefins by chromium-catalyzed allene semi-hydrogenation,

[0033] The allene compound is used as a raw material, the side arm is a cyclic (alkyl) (amino) carbene chromium complex substituted with diphenylphosphine as a catalyst, and hydrogen is used as a hydrogen source to fully react to obtain a trans-olefin;

[0034] The catalyst structure is as follows:

[0035]

[0036] The structure of allene compounds is as follows:

[0037]

[0038] Where: R 1 Selected from one of the following groups:

[0039] naphthyl, 4-methylphenyl, 4-ethylphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 4-benzyloxyphenyl, 4-(4-bromobenzyloxy)phenyl, 4-(3-chlorobenzyloxy)phenyl, 4-(4-fluorobenzyloxy)phenyl, 4-(3-nitrobenzyloxy)phenyl, 4-(nitrilemethoxy)phenyl, 4-(3-methylbut-2-en-1-yloxy)phenyl, 4-(pyridine-2-methoxy)phenyl, 4-methoxycarbonylmethoxyphenyl, 4-(tert-butyldimethylsilyloxy)phenyl, 4-(cyclopropanemethoxy)phenyl, 4-(phenoxy)phenyl, 4-biphenyl, 4-(4-tert-butylphenyl)benzene phenyl, 4-(4-(trifluoromethyl)phenyl)phenyl, 4-(4-(trifluoromethoxy)phenyl)phenyl, 4-(4-(trimethylsilyl)phenyl)phenyl, 4-(3-fluoro-4-methoxyphenyl)phenyl, 4-(2-methylthiophenyl)phenyl, 4-(furan-3-yl)phenyl, 4-(thiophen-3-yl)phenyl, 4-(1-H-pyrazol-1-yl)phenyl, 2,3-dihydrobenzofuran-6-yl, benzo[d][1,3]dioxolan-5-yl, 4-(benzo[d][1,3]dioxolan-5-yl)phenyl, 4-dimethylaminophenyl, 4-tert-butyloxycarbonylaminophenyl;

[0040] R 2 One selected from the following groups: hydrogen, methyl, ethyl, propyl, butyl;

[0041] R 3 One selected from the following groups: hydrogen, ethyl, butyl, benzyl, trimethylsilyl;

[0042] R 4 For hydrogen.

[0043] In the reaction process, magnesium is used as a reducing agent, and an additive is also included, and the additive is chlorosilane. The reaction temperature is 40-70°C, the hydrogen pressure is 1-4MPa, and the reaction time is 12-24h. The amount of the catalyst is 1%-5% of the molar amount of the allene compound. The chlorosilane is one of trimethylchlorosilane, triethylchlorosilane, dimethylchlorohydrosilane, and diphenylchlorohydrosilane. The molar ratio of magnesium to the allene compound is 0.5-2:1. The molar ratio of chlorosilane to the allene compound is 0.5-2:1.

[0044] Example 1

[0045] A method for preparing trans-olefins by chromium-catalyzed allene semi-hydrogenation comprises the following steps:

[0046] Under nitrogen atmosphere, Figure 2The allene (72 mg, 0.4 mmol) shown in 1a, catalyst (5.6 mg, 0.008 mmol), elemental magnesium (7.2 mg, 0.3 mmol), trimethylsilyl chloride (22 mg, 0.2 mmol) and tetrahydrofuran (2 mL) were placed in a test tube and then transferred to a high-pressure reactor. The mixture was stirred in an oil bath at 50°C for 12 hours under a hydrogen pressure of 3 MPa. After the reaction, the mixture was quenched with aqueous hydrochloric acid and extracted with ethyl acetate. The extract was freed from volatile solvents under reduced pressure and separated and purified by silica gel column chromatography. Petroleum ether was used as the eluent to obtain a colorless oily olefin 2a, the structure of which is shown below. The yield was 65 mg, the yield was 89%, and E / Z=99:1.

[0047]

[0048] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ = 7.85–7.77 (m, 4H), 7.60 (dd, J = 8.64, 1.76, 1H), 7.49–7. 40(m,2H),6.09–6.02(m,1H),2.14–2.12(m,3H),1.86(dd,J=6.96,1.60Hz,3H); 13 C NMR (100MHz, CDCl3): δ=141.2,135.4,133.6,132.4,128.0,127.6,127.5,126.0,125.4,124.4,123.8,123.2,15.5,14.5.HRMS (ESI + ):calcd for C 14 H 15 [M+H] + 183.1168, found 183.1162.

[0049] Example 2

[0050] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 The olefin 2b was obtained as a colorless oil, the structure of which is shown below, with a yield of 47 mg and a yield of 81%, E / Z = 99:1.

[0051]

[0052] The tested parameters are as follows: 1H NMR (400MHz, CDCl3): δ = 7.31 (d, J = 8.24Hz, 2H), 7.15 (d, J = 8.00Hz, 2H), 5.86–5.78 (m, 1H), 2.32 (s, 3H), 2.01–1.96 (m, 3H), 1.80–1.75 (m, 3H); 13 CNMR (100MHz, CDCl3): δ=141.2,136.0,135.4,128.9,125.4,121.6,21.0,15.5,14.3.HRMS (ESI + ):calcd for C 11 H 15 [M+H] + 147.1168, found 147.1163.

[0053] Example 3

[0054] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 The olefin 2c was obtained as a colorless oil, the structure of which is shown below, with a yield of 53 mg and a yield of 81%, E / Z = 99:1.

[0055]

[0056] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ = 7.32 (d, J = 8.32Hz, 2H), 7.16 (d, J = 8.32Hz, 2H), 5.87–5.80 (m, 1H),2.65(q,J=7.56,2H),2.02-2.00(m,3H),1.80–1.76(m,3H),1.26(t,J=7.56,3H); 13 C NMR (100MHz, CDCl3): δ=142.4,141.4,135.3,127.6,125.4,121.7,28.4,15.6,15.5,14.3.HRMS (ESI + ):calcd for C 12 H 17 [M+H] + 161.1325, found 161.1328.

[0057] Example 4

[0058] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 21d is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 50:1. The olefin 2d is obtained as a colorless oil, and its structure is shown below. The yield is 56 mg, the yield is 80%, and E / Z=97:3.

[0059]

[0060] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ=7.22–7.17(m,1H),6.76–6.71(m,1H),6.69(dt,J=7.56,1.36Hz,1H),6.65(dd,J=2.7 2,1.24Hz,1H),5.49–5.42(m,1H),3.76(s,3H),2.31–2.24(m,2H),1.51–1.49(m,3H),0.91(t,J=7.36Hz,3H); 13 C NMR (100MHz, CDCl3): δ=159.3,143.3,142.8,128.9,121.0,119.9,114.3,111.5,55.2,32.0,14.6,13.1.HRMS (ESI + ):calcd for C 12 H 17 O[M+H] + 177.1274, found 177.1270.

[0061] Example 5

[0062] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1e is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 50:1. The olefin 2e is obtained as a colorless oil, and its structure is shown below. The yield is 72 mg, the yield is 88%, and E / Z=94:6.

[0063]

[0064] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ = 7.08 (d, J = 8.68Hz, 2H), 6.88 (d, J = 8.80Hz, 2H), 5.56–5.49 (m, 1H), 3.84 (s ,3H),2.36–2.29(m,2H),1.58(dt,J=6.84,1.36Hz,3H),1.30–1.26(m,4H),0.86(t,J=6.96Hz,3H); 13C NMR (100MHz, CDCl3): δ=158.0,141.4,133.4,129.5,120.6,113.3,55.2,39.0,30.5,22.3,14.7,13.9.HRMS (ESI + ):calcd for C 14 H 21 O[M+H] + 205.1587, found 205.1588.

[0065] Example 6

[0066] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1f is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 100:1. The olefin 2f is obtained as a colorless oil, and its structure is shown below. The yield is 85 mg, the yield is 89%, and E / Z=94:6.

[0067]

[0068] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ=7.46–7.24(m,7H),6.98–6.85(m,2H),5.87–5.65(m,1H),5.03(s,2H),1.98(s,3H),1.76(dd,J=6.84,0.82Hz,3H); 13 C NMR (100MHz, CDCl3): δ=157.7,137.3,137.0,134.9,128.7,128.0,127.6,126.6,121.0,114.6,70.1,15.6,14.4.HRMS (ESI + ):calcd for C 17 H 19 O[M+H] + 239.1430, found 239.1438.

[0069] Example 7

[0070] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1 g is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 100:1. 2 g of colorless oily olefin is obtained, and its structure is shown below. The yield is 90 mg, the yield is 71%, and E / Z=95:5.

[0071]

[0072] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ = 7.51 (d, J = 8.42Hz, 2H), 7.31 (d, J = 8.82Hz, 4H), 6.99–6.79 ( m,2H),5.93–5.69(m,1H),5.01(s,2H),2.01(s,3H),1.79(dd,J=6.84,0.42Hz,3H); 13 C NMR (100MHz, CDCl3): δ=157.4,137.3,136.3,134.9,131.8,129.2,126.7,121.9,121.2,114.6,69.4,15.6,14.4.HRMS (ESI + ):calcd for C 17 H 18 BrO[M+H] + 317.0536, found 317.0538.

[0073] Example 8

[0074] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1h is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 100:1. The olefin 2h is obtained as a colorless oil, and its structure is shown below. The yield is 87 mg, the yield is 80%, and E / Z=93:7.

[0075]

[0076] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ = 7.46 (s, 1H), 7.36–7.28 (m, 5H), 6.96–6.87 (m, 2H), 5.87 –5.77(m,1H),5.04(s,2H),2.02(t,J=1.24Hz,3H),1.80(dd,J=6.82,1.0Hz,3H); 13 C NMR (100MHz, CDCl3): δ=157.4,139.4,137.3,134.9,134.6,123.0,128.1,127.5,126.7,125.5,121.2,114.6,69.3,15.6,14.4.HRMS (ESI + ):calcd for C 17 H18 ClO[M+H] + 273.1041, found 273.1042.

[0077] Example 9

[0078] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1i is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 100:1. The olefin 2i is obtained as a colorless oil, and its structure is shown below. The yield is 93 mg, the yield is 90%, and E / Z=91:9.

[0079]

[0080] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ=7.48–7.38(m,2H),7.37–7.28(m,2H),7.14–7.03(m,2H),6.97–6.89( m,2H),5.87–5.73(m,1H),5.03(s,2H),2.02(t,J=1.24Hz,3H),1.80(dd,J=6.82,1.02Hz,3H); 13 C NMR (100MHz, CDCl3): δ = 162.6 (d, J = 244.5Hz), 157.5, 137.2, 134.9, 133.0 (d, J = 3.2H z),129.4(d,J=8.3Hz),126.7,121.2,115.6(d,J=21.5Hz),114.6,69.5,15.6,14.4; 19 F NMR (376MHz, CDCl3): δ = -114.32.HRMS (ESI + ):calcd for C 17 H 18 FO[M+H] + 257.1336, found 257.1336.

[0081] Example 10

[0082] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1j is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 5:1. The olefin 2j is obtained as a colorless oil, and its structure is shown below. The yield is 100 mg, the yield is 88%, and E / Z=93:7.

[0083]

[0084] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ = 8.32 (s, 1H), 8.21–8.13 (m, 1H), 7.81–7.72 (m, 1H), 7.56 (t, J = 8.02Hz, 1H), 7.35–7 .29(m,2H),6.97–6.87(m,2H),5.90–5.70(m,1H),5.15(s,2H),2.01(t,J=0.84Hz,3H)),1.84–1.72(m,3H); 13 C NMR (100MHz, CDCl3): δ=157.0,148.6,139.5,137.7,134.8,133.2,129.7,126.8,123.0,122.3,121.4,114.6,68.8,15.6,14.4.HRMS (ESI + ):calcd for C 17 H 18 NO3[M+H] + 284.1281, found 284.1283.

[0085] Embodiment 11

[0086] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 The olefin 2k was obtained as a colorless oil, the structure of which is shown below, with a yield of 64 mg and a yield of 86%, E / Z = 90:10.

[0087]

[0088] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ=7.39–7.32(m,2H),6.99–6.85(m,2H),5.92–5.73(m,1H),4.75(s,2H),2.04–1.96(m,3H),1.87–1.75(m,3H); 13 C NMR (100MHz, CDCl3): δ=155.4,139.3,134.6,127.0,122.2,115.4,114.8,53.9,15.6,14.4.HRMS (ESI + ):calcd for C 12 H 14 NO[M+H] +188.1070, found 188.1070.

[0089] Example 12

[0090] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 The olefin 21 was obtained as a yellow oil, the structure of which is shown below, with a yield of 68 mg and a yield of 79%, E / Z = 96:4.

[0091]

[0092] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ=7.35–7.29(m,2H),6.92–6.83(m,2H),5.87–5.74(m,1H),5.59– 5.46(m,1H),4.52(d,J=6.82Hz,2H),2.06–1.99(m,3H),1.85–1.78(m,6H),1.76(s,3H); 13 C NMR (100MHz, CDCl3): δ=157.8,138.1,136.7,135.0,126.6,120.9,112.0,114.4,64.9,25.9,18.3,15.6,14.4.HRMS (ESI + ):calcd for C 15 H 21 O[M+H] + 217.1587, found 217.1588.

[0093] Example 13

[0094] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1m is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 20:1. The olefin 2m is obtained as a yellow solid, and its structure is shown below. The yield is 84 mg, the yield is 88%, and E / Z=93:7.

[0095]

[0096] The tested parameters are as follows: 1H NMR (400MHz, CDCl3): δ=7.35–7.29(m,2H),6.92–6.83(m,2H),5.87–5.74(m,1H),5.59– 5.46(m,1H),4.52(d,J=6.84Hz,2H),2.06–1.99(m,3H),1.85–1.78(m,6H),1.76(s,3H); 13 C NMR (100MHz, CDCl3): δ=157.6,157.2,149.3,137.2,136.9,134.8,126.7,122.7,121.4,121.2,114.6,70.8,15.6,14.4.HRMS (ESI + ):calcd for C 16 H 18 NO[M+H] + 240.1383, found 240.1384.

[0097] Embodiment 14

[0098] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 The olefin 2n was obtained as a white solid, the structure of which is shown below, with a yield of 75 mg and a yield of 85%, E / Z=96:4.

[0099]

[0100] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ=7.34–7.27(m,2H),6.90–6.80(m,2H),5.83–5.73(m,1H),4.63(s,2H),3.80(s,3H),2.02–1.97(m,3H),1.81–1.74(m,3H); 13 CNMR (100MHz, CDCl3): δ=169.6,156.6,137.9,134.8,126.7,121.5,114.4,65.6,52.4,15.6,14.4.HRMS(ESI + ):calcd for C 13 H 17 O3[M+H] + 221.1172, found 221.1172.

[0101] Embodiment 15

[0102] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 The olefin 2o was obtained as a white oil, the structure of which is shown below, with a yield of 98 mg and a yield of 93%, E / Z = 94:6.

[0103]

[0104] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ = 7.28 (d, J = 8.68Hz, 2H), 6.84 (d, J = 8.68Hz, 2H), 5.82–5.74 (m,1H),2.01–1.96(m,3H),1.77(dd,J=6.8,0.8Hz,3H),0.98(s,9H),0.19(s,6H); 13 C NMR (100MHz, CDCl3): δ=154.5,137.2,135.0,126.5,121.0,119.8,25.9,18.4,15.6,14.4,-4.3.HRMS (ESI + ):calcd for C 16 H 27 OSi[M+H] + 263.1826, found 263.1828.

[0105] Example 16

[0106] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1p is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 100:1. The olefin 2p is obtained as a colorless oil, and its structure is shown below. The yield is 77 mg, the yield is 89%, and E / Z=90:10.

[0107]

[0108] The tested parameters are as follows: 1H NMR (400MHz, CDCl3): δ = 7.06 (d, J = 8.80Hz, 2H), 6.88 (d, J = 8.80Hz, 2H), 6.52–6.45 (m, 1H), 3.80 (d, J = 6.84Hz, 2H), 2.35–2.27 (m,2H),1.56(dt,J=6.84,1.36Hz,3H),0.94(t,J=7.44Hz,3H),0.75(t,J=7.48Hz,1H),0.67–0.61(m,2H),0.37–0.32(m,2H); 13 C NMR (100MHz, CDCl3): δ=157.5,142.9,133.4,129.5,119.4,114.0,72.7,32.1,14.7,13.2,10.4,3.19,3.17.HRMS (ESI + ):calcd for C 15 H 21 O[M+H] + 217.1587, found 217.1589.

[0109] Embodiment 17

[0110] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1q is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 100:1. The olefin 2q is obtained as a colorless oil, and its structure is shown below. The yield is 89 mg, the yield is 88%, and E / Z=90:10.

[0111]

[0112] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ=7.36–7.30(m,2H),7.12–7.07(m,3H),7.05–7.01(m,2H),6.99–6.94(m,2H),5.56–5. 49(m,1H),2.32–2.26(m,2H),1.58(dt,J=2.32,1.12Hz,3H),1.32(q,J=7.44Hz,2H),0.86(t,J=7.24Hz,3H); 13 C NMR (100MHz, CDCl3): δ=157.4,155.5,141.0,136.1,129.8,129.7,123.1,121.2,118.8,118.4,41.3,21.3,14.7,13.7.HRMS (ESI+ ):calcd for C 18 H 21 O[M+H] + 253.1587, found 253.1587.

[0113] Embodiment 18

[0114] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 The olefin 2r was obtained as a colorless oil, the structure of which is shown below, with a yield of 75 mg and a yield of 90%, E / Z = 91:9.

[0115]

[0116] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ=7.68–7.60(m,4H),7.48(t,J=7.32Hz,2H),7.38(t,J=7.56Hz, 1H),7.33(dd,J=8.12,1.72Hz,2H),5.69-5.61(m,1H),2.11(s,3H),1.73–1.69(m,3H); 13 C NMR (100MHz, CDCl3): δ=141.0,140.8,139.2,136.3,128.8,128.5,127.2,127.0,126.8,122.0,25.4,15.0.HRMS (ESI + ):calcd for C 16 H 17 [M+H] + 209.1325, found 209.1324.

[0117] Embodiment 19

[0118] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 The olefin 2s was obtained as a colorless oil, the structure of which is shown below, with a yield of 95 mg and a yield of 90%, E / Z = 98:2.

[0119]

[0120] The tested parameters are as follows: 1H NMR (400MHz, CDCl3): δ = 7.59–7.52 (m, 4H), 7.48 (d, J = 8.44Hz, 2H), 7.28 (d, J = 8. 32Hz,2H),5.63–5.56(m,1H),2.08–2.04(m,3H),1.68–1.63(m,3H),1.36(s,9H); 13 C NMR (100MHz, CDCl3): δ=150.1,140.5,139.1,138.1,136.3,128.5,126.7,126.6,125.7,121.9,34.5,31.4,25.3,15.0.HRMS (ESI + ):calcd for C 20 H 25 [M+H] + 265.1951, found 265.1951.

[0121] Embodiment 20

[0122] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 The olefin 2t was obtained as a white solid, the structure of which is shown below, with a yield of 99 mg and a yield of 80%, E / Z = 90:10.

[0123]

[0124] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ=7.70–7.66(m,4H),7.57(d,J=8.40Hz,2H),7.31(d,J=8.28Hz,2H),5.66–5.58(m,1H),2.08–2.04(m,3H),1.67–1.63(m,3H); 13 CNMR (100MHz, CDCl3): δ = 144.5, 141.9, 137.7, 136.1, 128.8, 127.7, 127.3, 127.2 (d, J = 6.19Hz), 126.9, 125.7 (q, J = 3.65Hz), 122.3, 25.3, 15.0; 19 F NMR (376MHz, CDCl3): δ = -62.4.HRMS (ESI + ):calcd for C 17 H 16 F3[M+H] +277.1199, found 277.1204.

[0125] Embodiment 21

[0126] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1u is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 100:1. The olefin 2u is obtained as a colorless oil, and its structure is shown below. The yield is 109 mg, the yield is 93%, and E / Z=97:3.

[0127]

[0128] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ = 7.61 (d, J = 8.68Hz, 2H), 7.53 (d, J = 8.44Hz, 2H), 7.30–7.25 (m, 4H), 5.64–5.57 (m, 1H), 2.08–2.03 (m, 3H), 1.67–1.63 (m, 3H); 13 CNMR (100MHz, CDCl3): δ = 148.6 (d, J = 1.82Hz), 141.3, 139.8, 137.8, 136.1, 128.7, 128.3, 126.7, 122.2, 121.2, 120.6 (d, J = 255.56Hz), 25.3, 15.0; 19 F NMR (376MHz, CDCl3): δ = -57.8.HRMS (ESI + ):calcd for C 17 H 16 F3O[M+H] + 293.1148, found 293.1146.

[0129] Embodiment 22

[0130] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 The olefin 2v was obtained as a colorless oil, the structure of which is shown below, with a yield of 96 mg and a yield of 86%, E / Z = 93:7.

[0131]

[0132] The tested parameters are as follows: 1H NMR (400MHz, CDCl3): δ = 7.65–7.63 (m, 4H), 7.61 (d, J = 6.60Hz, 2H), 7.32 (d, J = 8. 12Hz,2H),5.68–5.60(m,1H),2.11–2.09(m,3H),1.72–1.68(m,3H),0.32(s,9H); 13 C NMR (100MHz, CDCl3): δ=141.4,140.9,139.1,136.3,133.82,133.77,128.5,126.8,126.4,122.0,25.3,15.0,-1.0.HRMS (ESI + ):calcd for C 19 H 25 Si[M+H] + 281.1720, found 281.1725.

[0133] Embodiment 23

[0134] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1w is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 50:1. The olefin 2w is obtained as a colorless oil, and its structure is shown below. The yield is 90 mg, the yield is 88%, and E / Z=92:8.

[0135]

[0136] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ = 7.50 (d, J = 8.32Hz, 2H), 7.37–7.30 (m, 2H), 7.26 (d, J = 8.92Hz, 2H), 7 .02(t,J=8.56Hz,1H),5.63–5.56(m,1H),3.93(s,3H),2.06–2.04(m,3H),1.66–1.62(m,3H); 13 C NMR (100MHz, CDCl3): δ = 152.6 (d, J = 243.9Hz), 146.9 (d, J = 10.6Hz), 140.8, 137.7 (d, J = 1.8Hz), 136.2, 134.3 (d, J=6.2Hz),128.6,126.3,122.5(d,J=3.3Hz),122.0,114.7(d,J=18.6Hz),113.7(d,J=2.6Hz),56.4,25.3,15.0; 19FNMR (376MHz, CDCl3): δ = -135.2.HRMS (ESI + ):calcd for C 17 H 18 FO[M+H] + 257.1336, found 257.1336.

[0137] Embodiment 24

[0138] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1x is shown. Catalyst (8.4 mg, 0.012 mmol), reaction temperature is 60°C; eluent is petroleum ether / ethyl acetate, volume ratio is 20:1. Colorless oily olefin 2x is obtained, the structure of which is shown below, the yield is 92 mg, the yield is 91%, E / Z=98:2.

[0139]

[0140] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ=7.41–7.37(m,2H),7.35–7.31(m,1H),7.29–7.26(m,2H),7.2 4–7.17(m,2H),5.63–5.56(m,1H),2.38(s,3H),2.09–2.06(m,3H),1.69–1.65(m,3H); 13 C NMR (100MHz, CDCl3): δ=140.9,140.8,138.5,137.1,136.4,130.1,128.9,127.83,127.81,125.2,124.7,121.9,25.3,16.0,15.1.HRMS (ESI + ):calcdfor C 17 H 19 [M+H] + 255.1202, found 255.1204.

[0141] Embodiment 25

[0142] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 The olefin 2y was obtained as a colorless oil, the structure of which is shown below, with a yield of 74 mg and a yield of 94%, E / Z = 97:3.

[0143]

[0144] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ=7.74(s,1H),7.50–7.37(m,5H),6.75–6.68(m,1H),5.96–5.89(m,1H),2.06(s,3H),1.83(d,J=6.82Hz,3H); 13 C NMR (100MHz, CDCl3): δ=143.7,142.8,138.4,135.2,130.6,126.4,126.0,125.8,122.5,109.0,15.5,14.5.HRMS (ESI + ):calcd for C 14 H 15 O[M+H] + 199.1117, found 199.1120.

[0145] Embodiment 26

[0146] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 The olefin 2z was obtained as a colorless oil, the structure of which is shown below, with a yield of 79 mg and a yield of 92%, E / Z = 98:2.

[0147]

[0148] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ = 7.57 (d, J = 8.44Hz, 2H), 7.45–7.43 (m, 1H), 7.41–7.35 (m, 2H) ),7.24(d,J=8.32Hz,2H),5.63–5.55(m,1H),2.06–2.03(m,3H),1.66–1.62(m,3H); 13 C NMR (100MHz, CDCl3): δ=142.2,140.7,136.3,134.0,128.6,126.3,126.2,126.1,121.9,120.0,25.3,15.0.HRMS (ESI + ):calcd for C 14 H 15 S[M+H] + 215.0889, found 215.0890.

[0149] Embodiment 27

[0150] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1aa is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 100:1. The olefin 2aa is obtained as a colorless oil, and its structure is shown below. The yield is 72 mg, the yield is 91%, and E / Z=92:8.

[0151]

[0152] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ = 7.88 (d, J = 2.52Hz, 1H), 7.71 (d, J = 2.00Hz, 1H), 7.63–7.56 (m, 2H), 7 .45–7.39(m,2H),6.45–6.40(m,1H),5.94–5.85(m,1H),2.03(s,3H),1.80(d,J=6.88Hz,3H); 13 C NMR (100MHz, CDCl3): δ=142.2,140.9,138.6,134.6,126.6,126.4,122.8,118.9,107.5,15.4,14.4.HRMS (ESI + ):calcd for C 13 H 15 N2[M+H] + 199.1230, found 199.1229.

[0153] Embodiment 28

[0154] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1ab is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 100:1. The olefin 2ab is obtained as a colorless oil, and its structure is shown below. The yield is 62 mg, the yield is 89%, and E / Z=92:8.

[0155]

[0156] The tested parameters are as follows: 1H NMR (400MHz, CDCl3): δ = 7.21 (s, 1H), 7.11 (d, J = 8.24Hz, 1H), 6.72 (dd, J = 8.20, 2.62Hz, 1H), 5.83–5. 65(m,1H),4.55(td,J=8.6,2.8Hz,2H),3.27–3.12(m,2H),1.99(d,J=1.24Hz,3H),1.83–1.74(m,3H); 13 C NMR (100MHz, CDCl3): δ=159.0,137.1,135.4,126.9,125.4,122.3,120.7,108.8,71.4,29.9,15.9,14.4.HRMS (ESI + ):calcd for C 12 H 15 O[M+H] + 175.1117, found 175.1118.

[0157] Embodiment 29

[0158] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1ac is shown. Catalyst (8.4 mg, 0.012 mmol), reaction temperature is 60°C; eluent is petroleum ether / ethyl acetate, the volume ratio is 100:1. Colorless oily olefin 2ac is obtained, the structure of which is shown below, the yield is 86 mg, the yield is 85%, E / Z=91:9.

[0159]

[0160] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ = 7.48 (d, J = 8.32Hz, 2H), 7.24 (d, J = 8.44Hz, 2H), 7.09–7.05 (m,2H),6.87(d,J=7.92Hz,2H),5.98(s,2H),2.06–2.03(m,3H),1.66–1.62(m,3H); 13 C NMR (100MHz, CDCl3): δ=148.1,147.0,140.5,138.9,136.3,135.4,128.5,126.5,121.9,120.5,108.6,107.6,101.1,25.3,15.0.HRMS (ESI + ):calcd for C 17 H17 O[M+H] + 253.1223, found 253.1224.

[0161] Embodiment 30

[0162] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1ad is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 50:1. The olefin 2ad is obtained as a colorless oil, and its structure is shown below. The yield is 73 mg, the yield is 89%, and E / Z=99:1.

[0163]

[0164] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ = 6.78 (d, J = 7.80Hz, 1H), 6.64 (d, J = 1.56Hz, 1H), 6.60 (dd, J = 7.92, 1.72Hz, 1H), 5.95 (s, 2H) ,5.52-5.45(m,1H),2.28–2.22(m,2H),1.56(dt,J=6.84,1.24Hz,3H),1.30(q,J=7.48Hz,2H),0.85(t,J=7.20,3H); 13 CNMR (100MHz, CDCl3): δ=147.2,145.8,141.2,135.0,121.7,121.1,109.1,107.9,100.8,41.5,21.2,14.7,13.6.HRMS (ESI + ):calcd for C 13 H 17 O2[M+H] + 205.1223, found 205.1225.

[0165] Embodiment 31

[0166] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1ae is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 10:1. The olefin 2ae is obtained as a colorless oil, and its structure is shown below. The yield is 61 mg, the yield is 87%, and E / Z=91:9.

[0167]

[0168] The tested parameters are as follows:1 H NMR (400MHz, CDCl3): δ=7.42–7.27(m,2H),6.80–6.67(m,2H),5.89–5.69(m,1H),2.95(d,J=1.42Hz,6H),2.01(s,3H),1.79(d,J=6.84Hz,3H); 13 CNMR (100MHz, CDCl3): δ=149.6,135.1,132.7,126.3,119.4,112.6,40.9,15.5,14.4.HRMS (ESI + ):calcd for C 12 H 18 N[M+H] + 176.1434, found 176.1436.

[0169] Embodiment 32

[0170] The other steps of this example are the same as those of Example 1, except that the allene in Example 1 is replaced by an equimolar amount of Figure 2 1af is shown. The eluent is petroleum ether / ethyl acetate, and the volume ratio is 10:1. The olefin 2af is obtained as a colorless oil, and its structure is shown below. The yield is 81 mg, the yield is 82%, and E / Z=87:13.

[0171]

[0172] The tested parameters are as follows: 1 H NMR (400MHz, CDCl3): δ=7.46–7.15(m,4H),6.52(s,1H),5.86–5.76(m,1H),1.99(s,3H),1.77(d,J=6.86Hz,3H),1.51(s,9H); 13 C NMR (100MHz, CDCl3): δ=152.9,139.0,136.8,134.9,126.1,121.5,118.5,80.5,28.5,15.5,14.4.HRMS (ESI + ):calcd for C 15 H 22 NO2[M+H] + 248.1645, found 248.1645.

[0173] Embodiment 37

[0174] The other steps of this example are the same as those of Example 1, except that the amount of catalyst used is 5.6 mg, 0.008 mmol, to obtain olefin 2a with a yield of 65 mg and a yield of 89%, E / Z=99:1.

[0175] Embodiment 38

[0176] The other steps of this example are the same as those of Example 1, except that the amount of elemental magnesium used is 9.6 mg, 0.4 mmol. Olefin 2a is obtained with a yield of 64 mg and a yield of 87%, E / Z=99:1.

[0177] Embodiment 39

[0178] The other steps of this example are the same as those of Example 1, except that the amount of trimethylsilyl chloride used is 44 mg, 0.4 mmol, to obtain olefin 2a with a yield of 64 mg and a yield of 88%, E / Z=99:1.

[0179] Embodiment 40

[0180] The other steps of this example are the same as those of Example 1, except that an equimolar amount of dimethylsilyl chloride is used to replace the trimethylsilyl chloride in Example 1. Olefin 2a is obtained with a yield of 59 mg and a yield of 81%, and E / Z=99:1.

[0181] The allene compounds used in the present invention are all prepared by existing methods, such as 1k to 1n, 1p, 1q, 1y, 1z, 1aa, 1ac, 1ae, 1af, 1ah and 1ai. Figure 3 shown.

[0182] Under nitrogen atmosphere, olefin (10mmol), bromoform (15mmol), benzyltriethylammonium chloride (0.1mmol), sodium hydroxide aqueous solution (50wt%, 40mmol) and dichloromethane (15mL) were added to a flask (100mL) in sequence, and reacted at room temperature until the reaction was completed by thin layer chromatography. After the reaction was completed, the mixture was quenched with water, extracted with dichloromethane, and the extract was dried over anhydrous sodium sulfate and the volatile solvent was removed under reduced pressure. Subsequently, tetrahydrofuran (10mL) was added under nitrogen atmosphere, cooled to 0°C in an ice bath, and the corresponding alkylmagnesium bromide (15mmol) was slowly added dropwise, and reacted at room temperature until the reaction was completed by thin layer chromatography. After the reaction was completed, the mixture was quenched with hydrochloric acid aqueous solution, extracted with ethyl acetate, and the volatile solvent was removed from the extract under reduced pressure, and the desired target products 1k~1n, 1p, 1q, 1y, 1z, 1aa, 1ac, 1ae, 1af, 1ah and 1ai were purified by silica gel column chromatography.

[0183] 1k, yellow oil, eluent is petroleum ether. The parameters tested are as follows:1 H NMR (400MHz, CDCl3): δ=7.41–7.34(m,2H),7.01–6.87(m,2H),5.06(d,J=2.92Hz,2H),4.79(s,2H),2.22(t,J=3.16Hz,3H); 13 C NMR (100MHz, CDCl3): δ=208.3,136.3,129.1,127.2,125.6,99.7,76.8,54.6,21.1,16.8.HRMS (ESI + ):calcd for C 12 H 12 NO[M+H] + 186.0931, found 186.0932.

[0184] 1l, colorless oil, eluent is petroleum ether. The parameters tested are as follows: 1 H NMR (400MHz, CDCl3): δ=7.41–7.30(m,2H),7.01–6.93(m,2H),5.22–5.18(m,2H),4.72(t,J=6.82Hz,1H),2.06–1.99(m,3H),1.91–1.83(m,6H); 13 C NMR (100MHz, CDCl3): δ=208.2,136.1,128.8,126.7,125.0,120.7,102.8,99.7,76.8,25.6,18.1,15.5.HRMS (ESI + ):calcd for C 15 H 19 [M+H] + 215.1430, found 215.1431.

[0185] 1m, yellow solid, the eluent is petroleum ether / ethyl acetate, the volume ratio is 20:1. The parameters tested are as follows: 1 H NMR (400MHz, CDCl3): δ = 8.65 (d, J = 6.24Hz, 2H), 7.61 (d, J = 8.48Hz, 2H), 7.54 (d, J=6.24Hz,2H),7.46(d,J=8.52Hz,2H),5.10(t,J=3.32Hz,2H),1.18(t,J=7.34Hz 3H); 13CNMR (100MHz, CDCl3): δ=206.3,138.6,136.1,134.5,128.7,128.5,127.7,127.1,126.8,109.6,98.4,73.0,13.9.HRMS (ESI + ):calcd for C 15 H 14 NO[M+H] + 224.1070, found 224.1071.

[0186] 1n, yellow oil, eluent is petroleum ether. The parameters tested are as follows: 1 H NMR (400MHz, CDCl3): δ=7.37–7.29(m,2H),6.94–6.82(m,2H),5.12–5.06(m,2H),4.66(s,2H),3.85(s,3H),1.85–1.78(m,3H); 13 C NMR (100MHz, CDCl3): δ=208.2,156.4,135.1,132.2,128.4,127.2,106.0,79.2,15.6,14.4.HRMS (ESI + ):calcd for C 13 H 15 O3[M+H] + 219.1016, found 219.1019.

[0187] 1p, yellow oil, the eluent is petroleum ether / ethyl acetate, the volume ratio is 100:1. The parameters tested are as follows: 1 H NMR (400MHz, CDCl3): δ = 7.09 (d, J = 8.80Hz, 2H), 6.92 (d, J = 8.80Hz, 2H), 5.06 (d, J = 2.92Hz, 2H), 2.65 (q, J = 7.5 6,2H),2.34-2.27(m,2H),1.26(t,J=7.56,3H),0.77(t,J=7.48Hz,1H),0.67–0.61(m,2H),0.37–0.32(m,2H); 13 C NMR (100MHz, CDCl3): δ=208.1,136.5,128.9,127.5,125.4,99.9,77.1,32.1,14.7,13.2,10.4,3.19,3.12.HRMS (ESI + ):calcd for C 15 H 19O[M+H] + 215.1430, found 215.1430.

[0188] 1q, yellow oil, the eluent is petroleum ether / ethyl acetate, the volume ratio is 100:1. The parameters tested are as follows: 1 H NMR (400MHz, CDCl3): δ=7.36–7.16(m,9H),5.07(t,J=3.32Hz,2H),2.39–2.32(m,2H),1.62–1.51(m,2H),0.98(t,J=7.36Hz,3H); 13 C NMR (100MHz, CDCl3): δ=208.8,136.3,135.7,133.3,131.5,130.5,129.1,126.80,126.78,104.4,78.4,31.5,21.1,14.0.HRMS (ESI + ):calcd for C 18 H 19 O[M+H] + 251.1430, found 251.1432.

[0189] 1y, yellow solid, eluent is petroleum ether. The parameters tested are as follows: 1 H NMR (400MHz, CDCl3): δ = 7.68 (d, J = 7.02Hz, 1H), 7.38 (d, J = 8.44Hz, 2H), 7.25 (s, J = 7.02Hz ,1H),7.21(d,J=8.04Hz,2H),7.09(d,J=7.02Hz,1H),5.08(q,2H),2.08(t,J=3.02Hz,3H); 13 C NMR (100MHz, CDCl3): δ=209.1,167.0,133.4,129.1,127.6,125.6,124.4,122.5,100.9,96.3,78.2,16.3.HRMS (ESI + ):calcd for C 14 H 13 O[M+H] + 197.0961, found 197.0963.

[0190] 1z, yellow solid, eluent is petroleum ether. The parameters tested are as follows: 1H NMR (400MHz, CDCl3): δ = 7.66 (d, J = 7.02Hz, 1H), 7.35 (d, J = 8.44Hz, 2H), 7.22 (s, J = 7.02Hz ,1H),7.16(d,J=8.04Hz,2H),6.98(d,J=7.02Hz,1H),5.02(q,2H),2.03(t,J=3.02Hz,3H); 13 C NMR (100MHz, CDCl3): δ=208.7,166.7,133.1,128.8,127.1,125.2,123.9,122.1,99.8,96.3,77.9,15.8.HRMS (ESI + ):calcd for C 14 H 13 S[M+H] + 213.0732, found 213.0733.

[0191] 1aa, yellow solid, the eluent is petroleum ether / ethyl acetate, the volume ratio is 100:1. The parameters tested are as follows: 1 HNMR (400MHz, CDCl3): δ = 7.90 (d, J = 2.52Hz, 1H), 7.73 (d, J = 2.00Hz, 1H), 7.66–7.60 (m, 2H) ,7.47–7.40(m,2H),6.48–6.43(m,1H),5.98–5.87(m,1H),5.14–5.09(m,2H),2.06(m,3H); 13 C NMR (100MHz, CDCl3): δ=208.5,143.2,141.9,138.9,135.1,127.0,126.8,123.0,119.3,107.2,15.8.HRMS (ESI + ):calcd for C 13 H 13 N2[M+H] + 197.1073, found 197.1075.

[0192] 1ac, yellow solid, the eluent is petroleum ether / ethyl acetate, the volume ratio is 50:1. The parameters tested are as follows: 1HNMR (400MHz, CDCl3): δ = 7.57 (d, J = 7.00Hz, 2H), 7.25 (d, J = 7.00Hz, 2H), 6.97 (d, J = 1.7 6Hz, 1H), 6.94 (dd, J = 8.12, 2.00Hz, 1H), 6.51 (t, J = 3.12Hz, 1H), 5.09 (t, J = 3.32Hz, 2H); 13 C NMR (100MHz, CDCl3): δ=206.2,147.9,146.8,134.8,130.3,128.7,127.0,126.7,119.2,109.8,106.9,101.0,97.9,77.8,14.8.HRMS (ESI + ):calcd for C 17 H 15 O2[M+H] + 251.1067, found 251.1068.

[0193] 1ae, yellow solid, the eluent is petroleum ether / ethyl acetate, the volume ratio is 10:1. The parameters tested are as follows: 1 HNMR (400MHz, CDCl3): δ=7.46–7.30(m,2H),6.83–6.69(m,2H),5.13–5.08(m,2H),3.09(s,6H),2.08–2.01(m,3H); 13 C NMR (100MHz, CDCl3): δ=208.3,149.3,135.6,132.9,126.8,119.7,112.5,41.2,14.7.HRMS (ESI + ):calcd for C 12 H 16 N[M+H] + 174.1277, found 174.1279.

[0194] 1af, yellow solid, the eluent is petroleum ether / ethyl acetate, the volume ratio is 10:1. The parameters tested are as follows: 1 HNMR (400MHz, CDCl3): δ = 7.46 (d, J = 8.68Hz, 2H), 7.35 (d, J = 8.66Hz, 2H), 7.16 (br, 1H), 5.02 (q, J = 3.12Hz, 2H), 2.19 (s, 9H), 2.09 (t, J = 3.08Hz, 3H); 13C NMR (100MHz, CDCl3): δ=208.8,168.1,136.3,132.7,126.2,119.7,99.3,76.6,24.7,22.3,16.7.HRMS (ESI + ):calcdfor C 15 H 20 NO2[M+H] + 246.1489, found 246.1491.

[0195] 1ah, yellow solid, eluent is petroleum ether. The parameters tested are as follows: 1 H NMR (400MHz, CDCl3): δ=7.60–7.53(m,4H),7.48–7.42(m,2H),7.39–7.34(m,2H),6. 18–6.12(m,1H),6.14–6.10(m,1H),2.57(q,J=6.72Hz,1H),0.92(t,J=7.32Hz,3H); 13 C NMR (100MHz, CDCl3): δ=206.3,141.0,139.6,134.2,128.9,127.4,127.3,127.2,127.1,93.8,89.8,22.3,13.9.HRMS (ESI + ):calcd for C 17 H 17 [M+H] + 221.1325, found 221.1328.

[0196] 1ai, yellow solid, eluent is petroleum ether. The parameters tested are as follows: 1 H NMR (400MHz, CDCl3): δ = 7.63 (dd, J = 8.12, 1.22Hz, 2H), 7.62–7.59 (m, 4H), 7.58 (d, J = 8.20Hz, 2H), 7.47 (t, J = 7.70Hz, 2H), 7.40 ( d,J=8.36Hz,2H),7.37(t,J=7.44Hz,1H),6.22–6.18(m,1H),6.16–6.11(m,1H),5.66–5.61(m,1H),2.04(dd,J=7.12,3.20,2H); 13C NMR (100MHz, CDCl3): δ=206.3,141.7,139.6,136.6,134.2,128.9,128.3,127.4,127.3,127.2,127.1,125.7,125.6,93.8,89.8,13.2.HRMS (ESI + ):calcd for C 22 H 19 [M+H] + 283.1481, found 283.1483.

[0197] In view of the limitations of the prior art, the present invention provides a method for preparing trans-olefin compounds by semi-hydrogenation of allenes without directing group substitution, which has mild conditions, cheap catalysts, wide sources of raw materials, simple operation, good regio- and stereo-selectivity.

Claims

1. A method for preparing trans-olefins by chromium-catalyzed allene semi-hydrogenation, characterized in that: The allene compound is used as a raw material, the side arm is a cyclic (alkyl) (amino) carbene chromium complex substituted with diphenylphosphine as a catalyst, and hydrogen is used as a hydrogen source to fully react to obtain a trans-olefin; The catalyst structure is as follows:

2. The method for preparing trans-olefins by chromium-catalyzed allene semi-hydrogenation according to claim 1, characterized in that: The structure of the allene compound is as follows: Where: R 1 Selected from one of the following groups: naphthyl, 4-methylphenyl, 4-ethylphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 4-benzyloxyphenyl, 4-(4-bromobenzyloxy)phenyl, 4-(3-chlorobenzyloxy)phenyl, 4-(4-fluorobenzyloxy)phenyl, 4-(3-nitrobenzyloxy)phenyl, 4-(nitrilemethoxy)phenyl, 4-(3-methylbut-2-en-1-yloxy)phenyl, 4-(pyridine-2-methoxy)phenyl, 4-methoxycarbonylmethoxyphenyl, 4-(tert-butyldimethylsilyloxy)phenyl, 4-(cyclopropanemethoxy)phenyl, 4-(phenoxy)phenyl, 4-biphenyl, 4-(4-tert-butylphenyl)benzene phenyl, 4-(4-(trifluoromethyl)phenyl)phenyl, 4-(4-(trifluoromethoxy)phenyl)phenyl, 4-(4-(trimethylsilyl)phenyl)phenyl, 4-(3-fluoro-4-methoxyphenyl)phenyl, 4-(2-methylthiophenyl)phenyl, 4-(furan-3-yl)phenyl, 4-(thiophen-3-yl)phenyl, 4-(1-H-pyrazol-1-yl)phenyl, 2,3-dihydrobenzofuran-6-yl, benzo[d][1,3]dioxolan-5-yl, 4-(benzo[d][1,3]dioxolan-5-yl)phenyl, 4-dimethylaminophenyl, 4-tert-butyloxycarbonylaminophenyl; R 2 One selected from the following groups: hydrogen, methyl, ethyl, propyl, butyl; R 3 One selected from the following groups: hydrogen, ethyl, butyl, benzyl, trimethylsilyl; R 4 For hydrogen.

3. The method for preparing trans-olefins by chromium-catalyzed semi-hydrogenation of allenes according to claim 1, characterized in that: In the reaction process, magnesium is used as a reducing agent and an additive is also included.

4. The method for preparing trans-olefins by chromium-catalyzed semi-hydrogenation of allenes according to claim 1, characterized in that: The reaction temperature is 40-70° C., the hydrogen pressure is 1-4 MPa, and the reaction time is 12-24 hours.

5. The method for preparing trans-olefins by chromium-catalyzed semi-hydrogenation of allenes according to claim 1, characterized in that: The amount of the catalyst used is 1% to 5% of the molar amount of the allene compound.

6. The method for preparing trans-olefins by chromium-catalyzed semi-hydrogenation of allenes according to claim 3, characterized in that: The additive is chlorosilane.

7. The method for preparing trans-olefins by chromium-catalyzed allene semi-hydrogenation according to claim 6, characterized in that: The chlorosilane is one of trimethylchlorosilane, triethylchlorosilane, dimethylchlorohydrosilane and diphenylchlorohydrosilane.

8. The method for preparing trans-olefins by chromium-catalyzed allene semi-hydrogenation according to claim 3, characterized in that: The molar ratio of magnesium to allene compound is 0.5 to 2:

1.

9. The method for preparing trans-olefins by chromium-catalyzed allene semi-hydrogenation according to claim 6, characterized in that: The molar ratio of the chlorosilane to the allene compound is 0.5 to 2:1.

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