A method for preparing trans-olefins by chromium-catalyzed semi-hydrogenation of allenes

Abstract

The present invention discloses a method for preparing trans-olefins by chromium-catalyzed semi-hydrogenation of allenes. The method uses an allene compound as a raw material, a cyclic (alkyl)(amino)carbene chromium complex with a diphenylphosphine-substituted side arm as a catalyst, and hydrogen as a hydrogen source, and undergoes a full reaction to obtain the trans-olefin. The method has mild preparation conditions, low cost, a wide range of raw material sources, simple operation, good regio- and stereoselectivity, and can be carried out without the need for a directing group.

Description

Technical Field

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

[0002] Allenes, due to their shared carbon atom between two carbon-carbon double bonds, exhibit unique physical and chemical properties, making them widely used in natural product synthesis, medicinal chemistry, and materials science. Given their wide availability, their conversion has attracted considerable attention. Methods for preparing olefin compounds using allenes can be categorized into methods using hydrogen as the hydrogen source and those using non-hydrogen as the hydrogen source, depending on the source of hydrogen.

[0003] Using non-hydrogen hydrogen sources, semi-reduction of some allenes is typically achieved using equivalent sodium / liquid nitrogen, hydrazines, and diisobutylaluminum hydride. However, this approach suffers from drawbacks such as a narrow substrate range, poor functional group compatibility, low yield, demanding reaction conditions, and poor selectivity. Furthermore, the use of equivalent reducing agents is associated with high cost and poor atom economy. Using water as a hydrogen source, heterogeneous palladium / carbon (Pd / C) catalysts mediated by boric acid can achieve selective semi-hydrogenation of 1,1-disubstituted allenes, but this suffers from low yields, a narrow substrate range, and poor stereoselectivity. Using formic acid as a hydrogen source, palladium catalysts, under ligand control, can achieve regioselective semi-hydrogenation of allenylamines to afford enamine and allylamine derivatives. Using diethyl malonate as a hydrogen source, semi-reduction of amino allenyl phosphates has been achieved via electrocatalytic reduction, but this reaction suffers from poor stereoselectivity. When Hantzsch ester is used as the 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, and a series of allyl compounds with chiral structures are obtained.

[0004] Using hydrogen as the gas source, the nonmetallic DABCO / B(C6F5)3 catalytic system can achieve the semi-hydrogenation of electron-deficient allenes. The homogeneous catalyst tris(triphenylphosphine)rhodium chloride (RhCl(PPh3)3) can achieve the semi-hydrogenation of some cyclic and acyclic allenes, providing regio- and stereoselective cis-alkenes. A bisimine-coordinated palladium catalyst (Pd(Ar-BIAN)(alkene)) utilizes the phosphonate, sulfonate, and carbonate groups on the allene as directing groups, achieving highly chemo-, regio-, and stereoselective semi-hydrogenation of allenes to synthesize the corresponding cis-alkenes. A heterogeneous palladium / carbon (Pd / C) catalyst has successfully achieved the semi-hydrogenation of α-phosphoramidate-based allenes, yielding a series of pharmaceutically active cis-α-phosphoramidate-based alkenes. Using a noble metal rhodium catalyst in combination with a chiral ligand and the directing effect of the sulfonyl group, a highly regioselective and enantioselective hemihydrogenation of tetrasubstituted allenyl sulfone compounds was achieved, resulting in the synthesis of a series of chiral allyl sulfone compounds. Using the abundant transition metal nickel as a catalyst and the directing effect of the sulfonyl group, the kinetic resolution of allenyl sulfone compounds was achieved, yielding enantiomerically enriched chiral trans-allyl sulfone compounds with high regioselectivity, stereoselectivity, and enantioselectivity.

[0005] While direct reduction using a metered non-hydrogen reducing agent and semi-reduction of allenes using a metered acid and organic hydrogen source under transition metal catalysis can achieve this, they suffer from disadvantages such as low atom economy, environmental concerns, and a dirty system. Using hydrogen as a hydrogen source and transition metal catalysis can achieve selective semi-hydrogenation of allenes economically and efficiently, these reactions are often substrate-specific, requiring, for example, the presence of a directing group in the allene. Summary of the Invention

[0006] In view of the problems existing in the prior art, the present invention provides a method for preparing trans-olefins by chromium-catalyzed semi-hydrogenation of allenes.

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

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

[0009] An allene compound is used as a raw material, a cyclic (alkyl)(amino)carbene chromium complex with a diphenylphosphine-substituted side arm is used 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] Furthermore, the structure of the allene compound is as follows:

[0013]

[0014] Where: R 1 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-(nitroxymethoxy)phenyl, 4-(3-methylbut-2-en-1-yloxy)phenyl, 4-(pyridin-2-methoxy)phenyl, 4-methoxycarbonylmethoxyphenyl, 4-(tert-butyldimethylsilyloxy)phenyl, 4-(cyclopropanemethoxy)phenyl, 4-(phenoxy)phenyl, 4-biphenylyl, 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-butoxycarbonylaminophenyl;

[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 additives are 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 raw material sources, simple operation, good regio- and stereoselectivity, 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 embodiment of the present invention.

[0030] Figure 3 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 with reference to the accompanying drawings and specific embodiments.

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

[0033] An allene compound is used as a raw material, a cyclic (alkyl)(amino)carbene chromium complex with a diphenylphosphine-substituted side arm is used 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 the allene compound is as follows:

[0037]

[0038] Where: R 1 One selected from 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-(nitroxymethoxy)phenyl, 4-(3-methylbut-2-en-1-yloxy)phenyl, 4-(pyridin-2-methoxy)phenyl, 4-methoxycarbonylmethoxyphenyl, 4-(tert-butyldimethylsilyloxy)phenyl, 4-(cyclopropanemethoxy)phenyl, 4-(phenoxy)phenyl, 4-biphenylyl, 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-butoxycarbonylaminophenyl;

[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] The reaction process uses magnesium as a reducing agent and includes an additive, which is chlorosilane. The reaction temperature is 40-70°C, the hydrogen pressure is 1-4 MPa, and the reaction time is 12-24 hours. The catalyst is used in an amount of 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 allene compound is 0.5-2:1. The molar ratio of chlorosilane to allene compound is 0.5-2:1.

[0044] Example 1

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

[0046] Under nitrogen atmosphere, Figure 2The allene 1a (72 mg, 0.4 mmol), 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 transferred to an autoclave. The mixture was stirred in an oil bath at 50°C under a hydrogen pressure of 3 MPa for 12 hours. After the reaction, the mixture was quenched with aqueous hydrochloric acid and extracted with ethyl acetate. The extract was freed from the volatile solvent under reduced pressure and purified by silica gel column chromatography using petroleum ether as eluent to afford olefin 2a as a colorless oil. The structure is shown below. The yield was 65 mg, with a yield of 89% and an E / Z ratio of 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,found183.1162.

[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% and an E / Z ratio of 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,found161.1328.

[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 used was petroleum ether / ethyl acetate in a volume ratio of 50:1. Olefin 2d was obtained as a colorless oil, the structure of which is shown below. The yield was 56 mg, with a yield of 80% and an E / Z ratio of 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 The elution solvent was petroleum ether / ethyl acetate in a volume ratio of 50:1. The olefin 2e was obtained as a colorless oil, the structure of which is shown below, in a yield of 72 mg, with a yield of 88% and an E / Z ratio of 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 used was petroleum ether / ethyl acetate in a volume ratio of 100:1. Olefin 2f was obtained as a colorless oil, the structure of which is shown below, in a yield of 85 mg, with a yield of 89% and an E / Z ratio of 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 of the compound was obtained as shown. The eluent was petroleum ether / ethyl acetate in a volume ratio of 100:1. 2 g of the olefin (90 mg) was obtained as a colorless oil, the structure of which is shown below. The yield was 71% and the E / Z ratio was 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,found317.0538.

[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 The elution solvent was petroleum ether / ethyl acetate in a volume ratio of 100:1. The olefin 2h was obtained as a colorless oil, the structure of which is shown below, in a yield of 87 mg, with a yield of 80% and an E / Z ratio of 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 forC 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 used was petroleum ether / ethyl acetate in a volume ratio of 100:1. The olefin 2i was obtained as a colorless oil, the structure of which is shown below, in a yield of 93 mg, a yield of 90%, and an E / Z ratio of 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 The eluent was petroleum ether / ethyl acetate in a volume ratio of 5:1. The olefin 2j was obtained as a colorless oil, the structure of which is shown below, in a yield of 100 mg with a yield of 88% and an E / Z ratio of 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,found284.1283.

[0085] Example 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% and an E / Z ratio of 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% and an E / Z ratio of 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 used was petroleum ether / ethyl acetate in a volume ratio of 20:1. The olefin 2m was obtained as a yellow solid, the structure of which is shown below. The yield was 84 mg, with a yield of 88% and an E / Z ratio of 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 forC 16 H 18 NO[M+H] + 240.1383, found 240.1384.

[0097] Example 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] Example 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% and an E / Z ratio of 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,found263.1828.

[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 The elution solvent was petroleum ether / ethyl acetate in a volume ratio of 100:1. The olefin 2p was obtained as a colorless oil, the structure of which is shown below, in a yield of 77 mg, with a yield of 89% and an E / Z ratio of 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] Example 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 The elution solvent was petroleum ether / ethyl acetate at a volume ratio of 100:1. The olefin 2q was obtained as a colorless oil, the structure of which is shown below, in a yield of 89 mg (88%) and an E / Z ratio of 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] Example 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,found209.1324.

[0117] Example 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% and an E / Z ratio of 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] Example 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] Example 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 The eluent was petroleum ether / ethyl acetate in a volume ratio of 100:1. The olefin 2u was obtained as a colorless oil, the structure of which is shown below, in a yield of 109 mg, a yield of 93%, and an E / Z ratio of 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] Example 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,found281.1725.

[0133] Example 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 The eluent was petroleum ether / ethyl acetate in a volume ratio of 50:1. The olefin 2w was obtained as a colorless oil, the structure of which is shown below, in a yield of 90 mg with a yield of 88% and an E / Z ratio of 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,found257.1336.

[0137] Example 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 The catalyst (8.4 mg, 0.012 mmol) was used, the reaction temperature was 60°C, and the eluent was petroleum ether / ethyl acetate in a volume ratio of 20:1. The olefin 2x was obtained as a colorless oil, the structure of which is shown below, in a yield of 92 mg, a yield of 91%, and an E / Z ratio of 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] Example 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] Example 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,found215.0890.

[0149] Example 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 The eluent was petroleum ether / ethyl acetate in a volume ratio of 100:1. The olefin 2aa was obtained as a colorless oil, the structure of which is shown below, in a yield of 72 mg, a yield of 91%, and an E / Z ratio of 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] Example 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 The eluent was petroleum ether / ethyl acetate in a volume ratio of 100:1. The olefin 2ab was obtained as a colorless oil, the structure of which is shown below, in a yield of 62 mg, with a yield of 89% and an E / Z ratio of 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] Example 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 The catalyst (8.4 mg, 0.012 mmol) was used, the reaction temperature was 60°C, and the eluent was petroleum ether / ethyl acetate in a volume ratio of 100:1. The olefin 2ac was obtained as a colorless oil, the structure of which is shown below, in a yield of 86 mg, 85% yield, and an E / Z ratio of 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 forC 17 H17 O[M+H] + 253.1223, found 253.1224.

[0161] Example 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 The eluent was petroleum ether / ethyl acetate in a volume ratio of 50:1. The olefin 2ad was obtained as a colorless oil, the structure of which is shown below, in a yield of 73 mg with a yield of 89% and an E / Z ratio of 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] Example 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 The eluent was petroleum ether / ethyl acetate in a volume ratio of 10:1. The olefin 2ae was obtained as a colorless oil, the structure of which is shown below, in a yield of 61 mg, with a yield of 87% and an E / Z ratio of 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] Example 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 The eluent was petroleum ether / ethyl acetate in a volume ratio of 10:1. The olefin 2af was obtained as a colorless oil, the structure of which is shown below, in a yield of 81 mg, with a yield of 82% and an E / Z ratio of 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] Example 37

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

[0175] Example 38

[0176] The other steps of this example were the same as those of Example 1, except that the amount of elemental magnesium used was 9.6 mg (0.4 mmol). Olefin 2a was obtained in a yield of 64 mg, a yield of 87%, and an E / Z ratio of 99:1.

[0177] Example 39

[0178] The other steps of this example were the same as those of Example 1, except that 44 mg (0.4 mmol) of trimethylsilyl chloride was used to obtain olefin 2a in a yield of 64 mg (88%) and an E / Z ratio of 99:1.

[0179] Example 40

[0180] The other steps of this example were the same as those of Example 1, except that an equal molar amount of dimethylchlorosilane was used to replace the trimethylchlorosilane in Example 1. Olefin 2a was obtained in a yield of 59 mg, a yield of 81%, and an E / Z ratio of 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 a nitrogen atmosphere, olefin (10 mmol), bromoform (15 mmol), benzyltriethylammonium chloride (0.1 mmol), aqueous sodium hydroxide solution (50 wt%, 40 mmol), and dichloromethane (15 mL) were added sequentially to a 100 mL flask and allowed to react at room temperature until the reaction was complete as monitored by thin-layer chromatography. After the reaction, the mixture was quenched with water and extracted with dichloromethane. The extract was dried over anhydrous sodium sulfate, and the volatile solvent was removed under reduced pressure. Subsequently, tetrahydrofuran (10 mL) was added under a nitrogen atmosphere, cooled to 0°C in an ice bath, and the corresponding alkylmagnesium bromide (15 mmol) was slowly added dropwise. The reaction was allowed to react at room temperature until the reaction was complete as monitored by thin-layer chromatography. After the reaction, the mixture was quenched with aqueous hydrochloric acid and extracted with ethyl acetate. 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 after testing 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,found215.1431.

[0185] 1m, yellow solid, 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,found224.1071.

[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, 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, 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, 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,found197.1075.

[0192] 1ac, yellow solid, 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,found251.1068.

[0193] 1ae, yellow solid, 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,found174.1279.

[0194] 1af, yellow solid, 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 raw material sources, simple operation, good regio- and stereoselectivity.

Claims

1. A method for preparing trans-olefins by chromium-catalyzed semi-hydrogenation of allenes, characterized in that: An allene compound is used as a raw material, a cyclic (alkyl)(amino)carbene chromium complex with a diphenylphosphine-substituted side arm is used 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: The structure of the allene compound is as follows: Where: R 1 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-(nitroxymethoxy)phenyl, 4-(3-methylbut-2-en-1-yloxy)phenyl, 4-(pyridin-2-methoxy)phenyl, 4-methoxycarbonylmethoxyphenyl, 4-(tert-butyldimethylsilyloxy)phenyl, 4-(cyclopropanemethoxy)phenyl, 4-(phenoxy)phenyl, 4-biphenylyl, 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-butoxycarbonylaminophenyl; 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 is hydrogen; In the reaction process, magnesium is used as a reducing agent, and an additive chlorosilane is also included. The chlorosilane is one of trimethylchlorosilane, triethylchlorosilane, dimethylchlorosilane and diphenylchlorosilane.

2. 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.

3. 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.

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

1.

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

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