A method for synthesizing chiral homoallylic alcohols by one-pot method under a copper-guanidine complex catalytic system

Abstract

The application discloses a method for synthesizing chiral homoallyl alcohol through a three-component one-pot series reaction catalyzed by a copper-guanidine complex. The method uses a conjugated diene, a boron reagent and an aldehyde compound as raw materials, and realizes efficient construction of an E configuration homoallyl alcohol structure with continuous chiral centers through proton boronation and allyl boronation series reaction under the action of the copper-guanidine complex. The method has the characteristics of simple reaction steps, wide applicability of raw materials, high yield and excellent stereoselectivity, and can effectively avoid the challenges in synthesis of a chiral allyl boron intermediate and low stability faced by traditional methods, thereby providing a simple and efficient synthesis route for preparation of homoallyl compounds with continuous chiral centers, and having good application prospect.

Description

Technical Field

[0001] This invention belongs to the field of chemical synthesis technology, specifically relating to a method for synthesizing chiral high-allyl alcohols through a one-pot tandem reaction of conjugated dienes, boron reagents, and aldehydes in a copper-guanidine complex catalytic system. Background Technology

[0002] Chiral homoallylic alcohols are key intermediates in the synthesis of numerous natural products and drug molecules, and their efficient and selective construction has always been an important research direction in the fields of organic synthesis and drug development. Among them, the asymmetric allylation reaction of carbonyl compounds is considered one of the simplest and most effective strategies for preparing chiral homoallylic alcohols. Allylboron compounds with defined double bond E / Z configurations and enantiomeric purity can undergo stereospecific addition with aldehyde groups via a six-membered ring chair transition state, and have advantages such as high functional group compatibility and low reagent toxicity, making them of great value in constructing homoallylic alcohol structures with continuous chiral centers.

[0003] However, existing technologies for preparing these structurally complex allylboron reagents suffer from cumbersome procedures and high costs. Furthermore, these compounds cannot be stored stably for extended periods, limiting their large-scale application in the synthesis of chiral high-allyl alcohols. In contrast, a one-pot, highly selective synthesis of chiral high-allyl alcohols using readily available and inexpensive conjugated dienes, boron sources, and aldehydes via a three-component tandem reaction involving double bond hydroboration and allyl addition avoids the need for pre-preparation of allylboron intermediates, making it more technologically attractive and promising for application.

[0004] Guanidinium structures exhibit strong σ-donor ligand behavior when coordinated with transition metals. Their conjugated structure effectively disperses the positive charge density of the central metal, forming stable electron-rich complexes. Simultaneously, the N-substituent side arms in the guanidinium structure enable efficient regio- and stereochemical control of the reaction. Existing research results indicate that, compared to conventional organophosphorus or carbene ligands, guanidinium compounds contribute to enhancing the nucleophilicity of the boron group on the central metal in transition metal-catalyzed olefin borylation reactions, thus providing satisfactory activity and selectivity. Using guanidinium compounds as catalyst ligands holds promise for achieving a one-pot asymmetric transformation of conjugated dienes, boron reagents, and aldehydes, directly preparing high-allyl alcohol compounds with continuous chiral centers, thus circumventing the constraint of requiring the pre-preparation of high-purity allyl boron reagent intermediates in existing technologies. Summary of the Invention

[0005] This invention aims to provide a method for constructing E-configuration homoallylic alcohols with continuous chiral centers in a one-pot process using conjugated dienes, boron reagents, and aldehyde compounds without the need for prior preparation of high-purity allyl boron reagents.

[0006] The technical solution of the present invention is as follows.

[0007] This invention discloses a method for synthesizing homoallyl alcohol by a one-pot tandem reaction of a conjugated diene, a boron reagent, and an aldehyde compound catalyzed by a copper-guanidine complex. The method utilizes a copper-guanidine complex formed by a copper salt and an N-substituted guanidine compound as catalysis. In the presence of a base and a proton source, and in an organic solvent, a selective proton borylation reaction of the conjugated diene followed by carbonyl addition to the aldehyde compound is performed to construct an E-configuration homoallyl alcohol structure with continuous chiral centers.

[0008] The copper salt is a copper(I) or copper(II) compound, wherein the copper(I) compound is selected from any one of cuprous chloride, cuprous bromide, cuprous iodide, cuprous acetate, cuprous hexafluorophosphate tetraacetonitrile, and cuprous thiophene-2-carboxylate, and the copper(II) compound is selected from any one of anhydrous copper chloride, copper chloride dihydrate, anhydrous copper sulfate, copper sulfate pentahydrate, copper nitrate trihydrate, and copper trifluoromethanesulfonate.

[0009] The N-substituted guanidine compounds have Figure 1 The general structures shown are preferably N,N'-bis(dipiperidinylmethylene)-(1S,2S)-cyclohexanediamine (Gua-1), (S)-N,N'-bis(dipiperidinylmethylene)-2,2'-diamino-1,1'-binaphthyl (Gua-2), N,N'-bis[bis(tetrahydropyrrolyl)methylene]-(1S,2S)-diphenylethylenediamine (Gua-3), N,N'-bis(dipiperidinylmethylene)-(1S,2S)-diphenylethylenediamine (Gua-4), and N,N'-bis[bis( Any one of the following: [hexamethyleneimino)methylene]-(1S,2S)-diphenylethylenediamine (Gua-5), N,N'-bis[di(4-methylpiperidinyl)methylene]-(1S,2S)-diphenylethylenediamine (Gua-6), N,N'-bis[di(1,2,3,4-tetrahydroquinoline)methylene]-(1S,2S)-diphenylethylenediamine (Gua-7), and N,N'-bis(dipiperidinylmethylene)-(1S,2S)-1,2-bis(4-fluorophenyl)ethylenediamine (Gua-8). The N-substituted guanidine compounds may also be guanidine salts of the above-described general structures, such as bis(hydrochloride) salts. Figure 1 The structures shown are merely illustrative examples and do not constitute a limitation on the scope of protection of this invention.

[0010] The conjugated diene is a linear endonucleoconjugated diene with a C1=C2–C3=C4 skeleton, and does not contain a terminal alkene (=CH2) structure. Figure 2The configuration or substitution shown. Wherein, the C1=C2 double bond is E or Z configuration, and the C3=C4 double bond is E or Z configuration. R1 is an aryl group. R2 is selected from either hydrogen or methyl. R3 is selected from either hydrogen or methyl. R4 is an alkyl group having 1-6 carbon atoms. Figure 2 The structures shown are merely illustrative examples and do not constitute a limitation on the scope of protection of this invention.

[0011] The boron reagent is selected from any one of tetrahydroxydiboron, bis(pinacol)diboron, and bis(neopentyl)diboron.

[0012] The aldehyde compound is selected from any one of benzaldehyde, 4-methylbenzaldehyde, 4-methoxybenzaldehyde, 4-chlorobenzaldehyde, 3-chlorobenzaldehyde, 2-chlorobenzaldehyde, 4-tert-butylbenzaldehyde, 1,4-benzodioxane-6-ylformaldehyde, cyclohexylformaldehyde, and n-hexanal.

[0013] The alkali is selected from any one of potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium ethoxide, sodium ethoxide, potassium methoxide, potassium hydroxide, sodium hydroxide, and lithium hydroxide.

[0014] The proton source is selected from any one of tert-butanol, sec-butanol, n-butanol, isopropanol, n-propanol, ethanol, methanol, and water.

[0015] The organic solvent is selected from any one or a mixture thereof, including n-hexane, n-pentane, n-heptane, n-octane, cyclohexane, toluene, p-xylene, m-xylene, o-xylene, chlorobenzene, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, methyl tert-butyl ether, cyclopentylmethyl ether, ethylene glycol dimethyl ether, 1,4-dioxane, dichloromethane, 1,2-dichloroethane, chloroform, acetonitrile, ethyl acetate, methanol, ethanol, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

[0016] Preferably, a one-pot method for synthesizing chiral homoallylic alcohols using a copper-guanidine complex catalysis involves adding a base, boron reagent, conjugated diene, aldehyde, proton source, copper salt, and the dihydrochloride salt of an N-substituted guanidine compound into a reaction vessel. After dissolving in an organic solvent, the mixture is stirred at a set temperature for a certain time to obtain a chiral homoallylic alcohol product with continuous chiral centers with high selectivity.

[0017] Preferably, in the method for one-pot synthesis of chiral high-allyl alcohols catalyzed by a copper-guanidine complex, the conjugated diene is a compound in the above general formula where the C1=C2 double bond is of E configuration, the C3=C4 double bond is of Z configuration, R2 and R3 are hydrogen, and R4 is methyl.

[0018] More preferably, in the method for one-pot synthesis of chiral high-allyl alcohols catalyzed by copper-guanidine complexes, the conjugated diene is selected from any of the following compounds, including (1E,3Z)-1-phenylpentan-1,3-diene, (1E,3Z)-1-(4-chlorophenyl)pentan-1,3-diene, (1E,3Z)-1-(3-chlorophenyl)pentan-1,3-diene, (1E,3Z)-1-(2-chlorophenyl)pentan-1,3-diene, (1E,3Z)-1-(3-fluorophenyl)pentan-1,3-diene, (1E,3Z)-1-(3,5-difluorophenyl)pentan-1,3-diene, (1E,3Z)-1-(4-fluoro-3-methylphenyl)pentan-1,3-diene, (1E... (1E,3Z)-1-(4-methoxyphenyl)pent-1,3-diene, (1E,3Z)-1-(3-methylphenyl)pent-1,3-diene, (1E,3Z)-1-(4-methylphenyl)pent-1,3-diene, (1E,3Z)-1-(4-ethylphenyl)pent-1,3-diene, (1E,3Z)-1-(4-propylphenyl)pent-1,3-diene, (1E,3Z)-1-(4-butylphenyl)pent-1,3-diene, (1E,3Z)-1-(2,4,6-trimethylphenyl)pent-1,3-diene, (1E,3Z)-1-(1-naphthyl)pent-1,3-diene, (1E,3Z)-1-(4-biphenyl)pent-1,3-diene.

[0019] Preferably, in the method for one-pot synthesis of chiral high-allyl alcohols catalyzed by a copper-guanidine complex, the boron reagent is bis(pinacol)diboron.

[0020] Preferably, in the method for one-pot synthesis of chiral high-allyl alcohols catalyzed by copper-guanidine complexes, the various aldehydes are selected from any of the following compounds, including benzaldehyde, 4-methylbenzaldehyde, 4-methoxybenzaldehyde, 4-chlorobenzaldehyde, 3-chlorobenzaldehyde, 2-chlorobenzaldehyde, 4-tert-butylbenzaldehyde, 1,4-benzodioxane-6-ylformaldehyde, cyclohexylformaldehyde, and n-hexanal.

[0021] Preferably, in the method for one-pot synthesis of chiral high-allyl alcohols catalyzed by a copper-guanidine complex, the copper salt is selected from any of the following compounds, including cuprous chloride, cuprous bromide, cuprous hexafluorophosphate tetraacetonitrile, cuprous thiophene-2-carboxylate, anhydrous copper chloride, and copper trifluoromethanesulfonate.

[0022] More preferably, in the method for one-pot synthesis of chiral high-allyl alcohols catalyzed by a copper-guanidine complex, the N-substituted guanidine compound is selected from any of the following compounds, including N,N'-bis[di(tetrahydropyrrolyl)methylene]-(1S,2S)-diphenylethylenediamine (Gua-3), N,N'-bis(dipiperidinylmethylene)-(1S,2S)-diphenylethylenediamine (Gua-4), N,N'-bis[di(hexamethyleneimino)methylene]-(1S,2S)-diphenylethylenediamine (Gua-5), and N,N'-bis(dipiperidinylmethylene)-(1S,2S)-1,2-bis(4-fluorophenyl)ethylenediamine (Gua-8).

[0023] Preferably, in the method for one-pot synthesis of chiral high-allyl alcohols catalyzed by copper-guanidine complexes, the ligand is a chiral biguanide compound having an N-substituted guanidine structure.

[0024] Preferably, in the method for one-pot synthesis of chiral high-allyl alcohols catalyzed by a copper-guanidine complex, the base is selected from any one of the following compounds, including potassium tert-butoxide, sodium tert-butoxide, potassium ethoxide, potassium methoxide, and potassium hydroxide.

[0025] Preferably, in the method for one-pot synthesis of chiral high-allyl alcohols catalyzed by a copper-guanidine complex, the proton source is selected from any of the following compounds, including isopropanol, n-propanol, ethanol, and methanol.

[0026] Preferably, in the method for one-pot synthesis of chiral high-allyl alcohols catalyzed by copper-guanidine complexes, the organic solvent is selected from any one or a mixture of the following compounds, including toluene, tetrahydrofuran, methyl tert-butyl ether, cyclopentyl methyl ether, ethylene glycol dimethyl ether, 1,4-dioxane, dichloromethane, and 1,2-dichloroethane.

[0027] Preferably, in the method for one-pot synthesis of chiral high-allyl alcohols catalyzed by a copper-guanidine complex, the molar ratio of the conjugated diene, boron reagent, and aldehyde is 1:2:2.

[0028] Preferably, in the method for one-pot synthesis of chiral high-allyl alcohols catalyzed by a copper-guanidine complex, the molar ratio of the conjugated diene, the proton source, and the base is 1:1.5:1.5.

[0029] Preferably, in the method for one-pot synthesis of chiral high-allyl alcohols catalyzed by copper-guanidine complexes, the amount of the copper salt and the N-substituted guanidine compound dihydrochloride salt is 5% of the molar amount of the conjugated diene.

[0030] Preferably, in the method for one-pot synthesis of chiral high-allyl alcohols catalyzed by copper-guanidine complexes, the reaction temperature is 25 °C and the reaction time is 24 h.

[0031] The beneficial effects and application value of this invention are:

[0032] This invention successfully realizes a one-pot method for synthesizing chiral high-allyl alcohols with continuous chiral centers via copper-guanidine complex catalysis, and successfully achieves a tandem reaction of asymmetric proton borylation and carbonyl allylation. This reaction system has advantages such as mild conditions, simple operation, low cost of raw materials and reagents, and ideal product yield, and exhibits excellent diastereoselectivity and enantioselectivity. Attached Figure Description

[0033] Figure 1 The general structure and preferred guanidine ligands of N-substituted guanidine compounds as described in this invention.

[0034] Figure 2 A schematic diagram of the conjugated diene structure as described in this invention.

[0035] Figure 3 A schematic diagram of the reaction for synthesizing (1S,2R,E)-2-benzyl-1-phenylpent-3-en-1-ol via the asymmetric proton borylation-carbonyl allylation tandem reaction described in this invention.

[0036] Figure 4 The proton NMR spectrum of (1S,2R,E)-2-benzyl-1-phenylpent-3-en-1-ol prepared by this invention ( 1 Figure of test results (H NMR, frequency: 400 MHz, solvent: CDCl3). Detailed Implementation

[0037] The technical solution of the present invention will be clearly and thoroughly described below with reference to specific embodiments and reaction formulas.

[0038] The following examples demonstrate the process of synthesizing chiral high-allyl products by a one-pot asymmetric tandem proton borylation-carbonyl allylation reaction of conjugated dienes, boron reagents and aldehydes under copper-guanidine complex catalytic conditions, with high diastereoselectivity and high enantioselectivity.

[0039] Example 1

[0040] As shown in Formula I below, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-benzyl-1-phenylpentan-3-en-1-ol:

[0041]

[0042] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar and sealed. The reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 40.4 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-phenylpent-3-en-1-ol, with a yield of 79%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 96:4.

[0043] Example 2

[0044] As shown in Formula II below, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and 4-methylbenzaldehyde as raw materials to prepare (1S,2R,E)-2-benzyl-1-(p-tolyl)pentan-3-en-1-ol via a catalytic asymmetric tandem proton borylation-carbonyl allylation reaction:

[0045]

[0046] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 48 mg 4-methylbenzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar and sealed. The reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 45.3 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-(p-tolyl)pent-3-en-1-ol, with a yield of 86%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 93:7.

[0047] Example 3

[0048] As shown in Formula III below, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and 4-methoxybenzaldehyde as raw materials to prepare (1S,2R,E)-2-benzyl-1-(4-methoxyphenyl)pentan-3-en-1-ol via a catalytic asymmetric tandem proton borylation-carbonyl allylation reaction:

[0049]

[0050] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 54.5 mg 4-methoxybenzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 39.5 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-(4-methoxyphenyl)pent-3-en-1-ol, with a yield of 71%, a diastereoselectivity greater than 99:1, and an enantioselectivity of 94:6.

[0051] Example 4

[0052] As shown in Formula IV below, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and 4-chlorobenzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-benzyl-1-(4-chlorophenyl)pentan-3-en-1-ol:

[0053]

[0054] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 56.2 mg 4-chlorobenzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 45.9 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-(4-chlorophenyl)pent-3-en-1-ol, with a yield of 78%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 93:7.

[0055] Example 5

[0056] As shown in equation V below, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and 3-chlorobenzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-benzyl-1-(3-chlorophenyl)pentan-3-en-1-ol:

[0057]

[0058] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 56.2 mg 3-chlorobenzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 48.4 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-(3-chlorophenyl)pent-3-en-1-ol, with a yield of 84%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 94:6.

[0059] Example 6

[0060] As shown in Formula VI below, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and 2-chlorobenzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-benzyl-1-(2-chlorophenyl)pentan-3-en-1-ol:

[0061]

[0062] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 56.2 mg 2-chlorobenzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar, and the flask was sealed. The reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 48.8 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-(2-chlorophenyl)pent-3-en-1-ol, with a yield of 87%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 93:7.

[0063] Example 7

[0064] As shown in Equation VII below, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and 4-tert-butylbenzaldehyde as raw materials to prepare (1S,2R,E)-2-benzyl-1-[4-(tert-butyl)phenyl]pentan-3-en-1-ol via a catalytic asymmetric tandem proton borylation-carbonyl allylation reaction:

[0065]

[0066] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 66.9 mg 4-tert-butylbenzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 46.3 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-[4-(tert-butyl)phenyl]pent-3-en-1-ol, with a yield of 75%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 94:6.

[0067] Example 8

[0068] As shown in Formula VIII below, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and 1,4-benzodioxane-6-carboxaldehyde as raw materials to prepare (1S,2R,E)-2-benzyl-1-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)pentan-3-en-1-ol via a catalytic asymmetric tandem proton borylation-carbonyl allylation reaction:

[0069]

[0070] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 65.7 mg 1,4-benzodioxane-6-carboxaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar, and the flask was sealed. The reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 49.7 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)pent-3-en-1-ol, with a yield of 82%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 92:8.

[0071] Example 9

[0072] As shown in Formula IX below, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and cyclohexylcarboxaldehyde as raw materials to prepare (1R,2R,E)-2-benzyl-1-cyclohexylpentan-3-en-1-ol via a catalytic asymmetric tandem proton borylation-carbonyl allylation reaction:

[0073]

[0074] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 44.9 mg cyclohexylformaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 46.5 mg of a pale yellow viscous liquid was obtained, which was the pure product (1R,2R,E)-2-benzyl-1-cyclohexylpent-3-en-1-ol, with a yield of 89%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 95:5.

[0075] Example 10

[0076] As shown in formula X below, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and n-hexanal as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (4R,5R,E)-4-benzyldec-2-en-5-ol:

[0077]

[0078] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 40.1 mg hexanal, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar, and the flask was sealed. The reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 25.1 mg of a pale yellow viscous liquid was obtained, which was the pure product (4R,5R,E)-4-benzyldec-2-en-5-ol, with a yield of 51%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 94:6.

[0079] Example 11

[0080] As shown in Equation XI below, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-benzyl-1-phenylpentan-3-en-1-ol:

[0081]

[0082] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 5.8 mg Gua-3 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 26.2 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-phenylpent-3-en-1-ol, with a yield of 52%, a diastereoselectivity ratio of 93:5, and an enantioselectivity ratio of 85:15.

[0083] Example 12

[0084] As shown in Formula XII below, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-benzyl-1-phenylpentan-3-en-1-ol:

[0085]

[0086] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 7.0 mg Gua-5 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 29.3 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-phenylpent-3-en-1-ol, with a yield of 58%, a diastereoselectivity ratio of 97:3, and an enantioselectivity ratio of 91:9.

[0087] Example 13

[0088] As shown in Formula XIII below, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-benzyl-1-phenylpentan-3-en-1-ol:

[0089]

[0090] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.8 mg Gua-8 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 36.8 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-phenylpent-3-en-1-ol, with a yield of 73%, a diastereoselectivity ratio of 98:2, and an enantioselectivity ratio of 93:7.

[0091] Example 14

[0092] As shown in Formula XIV below, this example uses (1E,3Z)-1-(4-chlorophenyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-(4-chlorobenzyl)-1-phenylpent-3-en-1-ol:

[0093]

[0094] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 35.6 mg (1E,3Z)-1-(4-chlorophenyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10). After concentration, 45.8 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-(4-chlorobenzyl)-1-phenylpent-3-en-1-ol, with a yield of 79%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 94:6.

[0095] Example 15

[0096] As shown in equation XV below, this example uses (1E,3Z)-1-(3-chlorophenyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-(3-chlorobenzyl)-1-phenylpent-3-en-1-ol:

[0097]

[0098] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 35.6 mg (1E,3Z)-1-(3-chlorophenyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 40.2 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-(3-chlorobenzyl)-1-phenylpent-3-en-1-ol, with a yield of 70%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 95:5.

[0099] Example 16

[0100] As shown in equation XVI below, this example uses (1E,3Z)-1-(2-chlorophenyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-(2-chlorobenzyl)-1-phenylpent-3-en-1-ol:

[0101]

[0102] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 35.6 mg (1E,3Z)-1-(2-chlorophenyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 41.9 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-(2-chlorobenzyl)-1-phenylpent-3-en-1-ol, with a yield of 73%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 95:5.

[0103] Example 17

[0104] As shown in Equation XVII below, this example uses (1E,3Z)-1-(3-fluorophenyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-(3-fluorobenzyl)-1-phenylpent-3-en-1-ol:

[0105]

[0106] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 32.4 mg (1E,3Z)-1-(3-fluorophenyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 38.4 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-(3-fluorobenzyl)-1-phenylpent-3-en-1-ol, with a yield of 71%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 93:7.

[0107] Example 18

[0108] As shown in Formula XVIII below, this example uses (1E,3Z)-1-(3,5-difluorophenyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-(3,4-difluorobenzyl)-1-phenylpent-3-en-1-ol:

[0109]

[0110] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 36.0 mg (1E,3Z)-1-(3,5-difluorophenyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 42.7 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-(3,5-difluorobenzyl)-1-phenylpent-3-en-1-ol, with a yield of 74%, a diastereoselectivity greater than 99:1, and an enantioselectivity of 91:9.

[0111] Example 19

[0112] As shown in Formula XIX below, this example uses (1E,3Z)-1-(4-fluoro-3-methylphenyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-(4-fluoro-3-methylbenzyl)-1-phenylpent-3-en-1-ol:

[0113]

[0114] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 35.2 mg (1E,3Z)-1-(4-fluoro-3-methylphenyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 44.4 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-(4-fluoro-3-methylbenzyl)-1-phenylpent-3-en-1-ol, with a yield of 78%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 93:7.

[0115] Example 20

[0116] As shown in formula XX below, this example uses (1E,3Z)-1-(4-methoxyphenyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-(4-methoxybenzyl)-1-phenylpent-3-en-1-ol:

[0117]

[0118] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 34.8 mg (1E,3Z)-1-(4-methoxyphenyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 42.4 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-(4-methoxybenzyl)-1-phenylpent-3-en-1-ol, with a yield of 75%, a diastereoselectivity greater than 99:1, and an enantioselectivity of 96:4.

[0119] Example 21

[0120] As shown in Formula XXI, this example uses (1E,3Z)-1-(3-methylphenyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-(3-methylbenzyl)-1-phenylpent-3-en-1-ol:

[0121]

[0122] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 31.6 mg (1E,3Z)-1-(3-methylphenyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 40.5 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-(3-methylbenzyl)-1-phenylpent-3-en-1-ol, with a yield of 76%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 93:7.

[0123] Example 22

[0124] As shown in Formula XXII below, this example uses (1E,3Z)-1-(4-methylphenyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-(4-methylbenzyl)-1-phenylpent-3-en-1-ol:

[0125]

[0126] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 31.6 mg (1E,3Z)-1-(4-methylphenyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 36.2 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-(4-methylbenzyl)-1-phenylpent-3-en-1-ol, with a yield of 68%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 91:9.

[0127] Example 23

[0128] As shown in Formula XXIII, this example uses (1E,3Z)-1-(4-ethylphenyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-(4-ethylbenzyl)-1-phenylpent-3-en-1-ol:

[0129]

[0130] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 34.4 mg (1E,3Z)-1-(4-ethylphenyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 44.3 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-(4-ethylbenzyl)-1-phenylpent-3-en-1-ol, with a yield of 79%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 92:8.

[0131] Example 24

[0132] As shown in Formula XXIV below, this example uses (1E,3Z)-1-(4-propylphenyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-(4-propylbenzyl)-1-phenylpent-3-en-1-ol:

[0133]

[0134] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 37.2 mg (1E,3Z)-1-(4-propylphenyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 44.8 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-(4-propylbenzyl)-1-phenylpent-3-en-1-ol, with a yield of 76%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 93:7.

[0135] Example 25

[0136] As shown in Equation XXV, this example uses (1E,3Z)-1-(4-butylphenyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-(4-butylbenzyl)-1-phenylpent-3-en-1-ol:

[0137]

[0138] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 40.0 mg (1E,3Z)-1-(4-butylphenyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar, and the flask was sealed. The reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 49.4 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-(4-butylbenzyl)-1-phenylpent-3-en-1-ol, with a yield of 80%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 93:7.

[0139] Example 26

[0140] As shown in Formula XXVI below, this example uses (1E,3Z)-1-(2,4,6-trimethylphenyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-1-phenyl-2-(2,4,6-trimethylbenzyl)pent-3-en-1-ol:

[0141]

[0142] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 37.2 mg (1E,3Z)-1-(2,4,6-trimethylphenyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar, and the flask was sealed. The reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 34.2 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-1-phenyl-2-(2,4,6-trimethylbenzyl)pent-3-en-1-ol, with a yield of 58%, a diastereoselectivity of 89:11, and an enantioselectivity of 93:7.

[0143] Example 27

[0144] As shown in Formula XXVII below, this example uses (1E,3Z)-1-(1-naphthyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-(naphthyl-1-methyl)-1-phenylpent-3-en-1-ol:

[0145]

[0146] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 38.8 mg (1E,3Z)-1-(1-naphthyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 48.4 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-(naphth-1-ylmethyl)-1-phenylpent-3-en-1-ol, with a yield of 80%, a diastereoselectivity greater than 99:1, and an enantioselectivity of 93:7.

[0147] Example 28

[0148] As shown in Formula XXVIII, this example uses (1E,3Z)-1-(4-biphenyl)pent-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-([1,1'-biphenyl]-4-ylmethyl)-1-phenylpent-3-en-1-ol:

[0149]

[0150] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 44.0 mg (1E,3Z)-1-(4-biphenyl)pent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar. The flask was sealed and the reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 53.9 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-([1,1'-biphenyl]-4-ylmethyl)-1-phenylpent-3-en-1-ol, with a yield of 82%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 92:8.

[0151] Example 29

[0152] As shown in Formula XXIX, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to catalyze an asymmetric tandem proton borylation-carbonyl allylation reaction to prepare (1S,2R,E)-2-benzyl-1-phenylpentan-3-en-1-ol:

[0153]

[0154] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous 1,4-dioxane were sequentially added to a 4 mL reaction flask equipped with a stir bar and sealed. The reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 32.8 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-phenylpent-3-en-1-ol, with a yield of 65%, a diastereoselectivity ratio of 98:2, and an enantioselectivity ratio of 89:11.

[0155] Example 30

[0156] As shown in the following formula XXX, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to prepare (1S,2R,E)-2-benzyl-1-phenylpentan-3-en-1-ol via a catalytic asymmetric tandem proton borylation-carbonyl allylation reaction:

[0157]

[0158] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.9 mg cuprous thiophene-2-carboxylate (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous methyl tert-butyl ether were sequentially added to a 4 mL reaction flask equipped with a stir bar, and the flask was sealed. The reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 30.3 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-phenylpent-3-en-1-ol, with a yield of 60%, a diastereoselectivity ratio of 98:2, and an enantioselectivity ratio of 87:13.

[0159] Example 31

[0160] As shown in formula XXXI, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to prepare (1S,2R,E)-2-benzyl-1-phenylpentan-3-en-1-ol via a catalytic asymmetric tandem proton borylation-carbonyl allylation reaction:

[0161]

[0162] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.4 mg cuprous bromide (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpent-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar, and the flask was sealed. The reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 35.3 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-phenylpent-3-en-1-ol, with a yield of 70%, a diastereoselectivity ratio greater than 99:1, and an enantioselectivity ratio of 93:7.

[0163] Example 32

[0164] As shown in formula XXXII, this example uses (1E,3Z)-1-phenylpentan-1,3-diene, bis(pinacolyl)diboron, and benzaldehyde as raw materials to prepare (1S,2R,E)-2-benzyl-1-phenylpentan-3-en-1-ol via a catalytic asymmetric tandem proton borylation-carbonyl allylation reaction:

[0165]

[0166] 33.7 mg potassium tert-butoxide (0.30 mmol), 102 mg bis(pinacol)diboron (0.40 mmol), 1.3 mg anhydrous copper chloride (0.01 mmol), 6.4 mg Gua-4 dihydrochloride (0.01 mmol), 9.6 mg methanol (0.30 mmol), 28.8 mg (1E,3Z)-1-phenylpentan-1,3-diene, 42.4 mg benzaldehyde, and 2 mL anhydrous dichloromethane were sequentially added to a 4 mL reaction flask equipped with a stir bar, and the flask was sealed. The reaction mixture was reacted at 25 °C for 24 h. After the reaction was completed, 2 mL of saturated brine was added to quench the reaction. The organic phase was removed, and the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove most of the organic solvent, yielding a crude product concentrate. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 100:5~10), and after concentration, 34.8 mg of a pale yellow viscous liquid was obtained, which was the pure product (1S,2R,E)-2-benzyl-1-phenylpent-3-en-1-ol, with a yield of 69%, a diastereoselectivity ratio of 97:3, and an enantioselectivity ratio of 90:10.

Claims

1. A method for synthesizing chiral homoallylic alcohols having continuous chiral centers, characterized in that, Using copper-guanidine complexes as catalysts, conjugated dienes, boron reagents, and aldehydes undergo an asymmetric one-pot tandem reaction in an organic solvent in the presence of a base and a proton source. The tandem reaction includes: (1) Asymmetric protonation of conjugated dienes, (2) The asymmetric carbonyl addition reaction of the generated chiral allylboron intermediate with aldehydes, Thus constructing a structure with continuous chiral centers E Configuration: high allyl alcohol.

2. The method according to claim 1, characterized in that, The copper-guanidine complex is formed by a metallic copper salt and an N-substituted guanidine compound.

3. The method according to claim 1 or 2, characterized in that, The copper salt is a copper(I) or copper(II) compound; The copper (I) compound is selected from one of cuprous chloride, cuprous bromide, cuprous iodide, cuprous acetate, cuprous hexafluorophosphate tetraacetonitrile, and cuprous thiophene-2-carboxylate. The copper(II) compound is selected from one of anhydrous copper chloride, copper chloride dihydrate, anhydrous copper sulfate, copper sulfate pentahydrate, copper nitrate trihydrate, and copper trifluoromethanesulfonate.

4. The method according to any one of claims 1-3, characterized in that, The N-substituted guanidine compounds are chiral biguanide compounds in which all amino groups in the guanidine group are completely substituted.

5. The method according to any one of claims 1-4, characterized in that, The conjugated diene is a linear intraconjugated diene with a C1=C2–C3=C4 skeleton, as shown in Figure 1, and does not contain a terminal alkene (=CH2) structure. in: The C1=C2 double bond has either an E or Z configuration. The C3=C4 double bond has either an E or Z configuration. R1 is aryl. R2 and R3 are hydrogen or methyl. R4 is an alkyl group having 1-6 carbon atoms.

6. The method according to any one of claims 1-5, characterized in that, The boron reagent is selected from bis(pinacol)diboron, bis(neopentyl)diboron, or tetrahydroxydiboron.

7. The method according to any one of claims 1-6, characterized in that, The aldehyde compounds are selected from aromatic aldehydes or aliphatic aldehydes.

8. The method according to any one of claims 1-7, characterized in that, The molar ratio of the conjugated diene, boron reagent, and aldehyde compound is 1:2:

2.

9. The method according to any one of claims 1-8, characterized in that, The amounts of the copper salt and the N-substituted guanidine compound are 5% of the amount of the conjugated diene, respectively.

10. The method according to any one of claims 1-9, characterized in that, The reaction temperature is 20-30 °C.

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