Direct deoxidation arylation method of fatty alcohol

Abstract

The invention discloses a direct deoxidization and arylation method of fatty alcohol, which comprises the following steps: in an organic solvent, in the presence of a photocatalyst, a nickel catalyst, a ligand, alkali, an additive, a deoxidization reagent and a molecular sieve, directly carrying out deoxidization and arylation reaction on an alcohol substrate and an aromatic substrate to obtain an arylation product of the corresponding alcohol, according to the method, the deoxidation arylation reaction is directly carried out by using the alcohol substrate, the corresponding arylation product can be obtained without preparing an intermediate product through pretreatment, and the method has the advantages of good substrate universality and functional group compatibility, high yield, good purity, low reaction cost, mild conditions and practicability.

Description

Technical Field

[0001] The present application relates to a method for direct deoxygenation arylation of fatty alcohols, belonging to the technical field of organic compound reduction. Background Art

[0002] The C-C bond is a core structural unit in the construction of molecular skeletons, and its efficient synthesis strategy has always been a research focus in the field of chemistry. Traditional synthesis methods rely on precious metal catalysts such as palladium (Pd) and ruthenium (Ru), which are subject to problems such as high cost, harsh conditions, and cumbersome post-processing. With the rise of green chemistry, new systems using dual catalysis of visible light and transition metals have become a breakthrough. Compared with other types of alkyl precursors, alcohol compounds have the advantages of being abundant in nature, inexpensive and readily available, and generally structurally stable, making them ideal substrates for constructing C-C bonds.

[0003] However, due to the low reactivity of alcohols, the hydroxyl group (-OH) is a poor leaving group (leaving ability is weaker than that of halogens or sulfonates), making it difficult to directly participate in coupling reactions. Pre-activation (such as conversion to sulfonates, halides, or borate esters) is usually required, which increases the number of reaction steps and complexity, and reduces the atom economy of the reaction. Currently available activation methods for alcohols include: (1) N-heterocyclic carbene (NHC)-mediated deoxygenation strategy; (2) activation strategy to convert alcohols into acetals; (3) esterification followed by deoxygenation of alcohols, such as oxalation and xanthate; (4) conversion of alcohols into phosphine oxide adducts; and (5) conversion of alcohols into bromides. Although the above methods are feasible, there are still some limiting factors, such as: (1) the synthesis steps of the activation reagent N-heterocyclic carbene (NHC) are complicated and the drugs used are expensive; (2) most photocatalytically mediated reaction systems use precious metal Ir catalysts; (3) the sulfide ions in the xanthate intermediates easily coordinate with the metal center to form a stable complex, and their strong interaction significantly inhibits the effective coupling of the two types of catalytic cycles; (4) the scope of substrate application is not wide enough, and the types of applicable reactions need to be further expanded.

[0004] In order to solve the above problems, it is important and necessary to develop a new alcohol C-OH activation mode that is suitable for primary, secondary and tertiary alcohols with low reaction cost, mild conditions and simple operation. Summary of the Invention

[0005] In view of this, the first aspect of the present application is to provide a method for direct deoxygenation arylation of fatty alcohols to achieve direct deoxygenation arylation reaction of fatty alcohols.

[0006] Specifically, this application is implemented through the following solutions:

[0007] A direct deoxyarylation method for fatty alcohols comprises the following steps: in an organic solvent, in the presence of a photocatalyst, a nickel catalyst, a ligand, a base, an additive, a deoxygenation agent, and a molecular sieve, and under visible light irradiation, directly subjecting an alcohol substrate and an aromatic substrate to a deoxyarylation reaction to obtain an arylated product of the corresponding alcohol.

[0008] The reaction expression corresponding to the above deoxyarylation reaction is:

[0009]

[0010] In the formula, R is any one of an alkyl group, a carbocyclic ring, a chain hydrocarbon containing an aromatic structure, a chain hydrocarbon containing a heteroatom (halogen, N, O, S), or a carbocyclic ring.

[0011] The alkyl group includes unsubstituted C1 to C 30 Alkyl or substituted C1~C 30 More preferably, the substituent of the substituted alkyl group is C6-C 10 Aryl, O-containing heterocycle, OH, OBz, COOEt, COOMe, CF3, OMe, OPh, Ph, OTBS, N, O, S, halogen, or any of CN.

[0012] The carbon ring is a 6- to 20-membered carbon ring connected by carbon-carbon bonds.

[0013] Preferably:

[0014] The alcohol substrate is

[0015] Any one of .

[0016] The aromatic substrate is Any one of .

[0017] The following reaction conditions can be used to obtain better reaction yields:

[0018] The molar concentration of the alcohol substrate in the organic solvent is 0.1 mol / L.

[0019] The molar concentration of the aromatic substrate in the organic solvent is 0.03 mol / L.

[0020] The organic solvent is selected from any one of DCE, DCM, PhCF3, DMF, DMSO, DMAc or a mixed solvent thereof, preferably DCE.

[0021] The photocatalyst is selected from any one of 4-CzIPN, 4-CzPN, 4-CzTPN, 4-DPAIPN, 4-DPAPN, and 4-DPATPN.

[0022] The nickel catalyst is selected from Ni(hfacac)2, Ni(TMHD)2, Ni(acac)2, Ni(hfacac)2, Any one of NiCl2·glyme, NiCl2·diglyme, NiBr2·diglyme, and NiBr2·glyme.

[0023] The ligand is preferably a terpyridine ligand.

[0024] The base is selected from any one of Na2CO3, Li2CO3, Na3PO4, Li3PO4, LiOAc, and NaOAc.

[0025] The additive is selected from any one of triphenylamine, diphenylamine, 4-methoxytriphenylamine, 4-bromotriphenylamine, 4,4',4"-trimethyltriphenylamine, LiI, and TBAI.

[0026] The deoxidation agent is selected from any one of sodium tetraphenylborate, lithium tetraphenylborate, ammonium tetraphenylborate, sodium tetra(4-methyl-phenyl)borate and sodium tetra(4-phenyl-phenyl)borate.

[0027] The molecular sieve is preferably an MS molecular sieve.

[0028] In the deoxyarylation reaction, the reaction temperature is room temperature and the reaction time is 4 to 12 hours.

[0029] The deoxyarylation reaction is carried out in the presence of visible light, preferably a blue LED with a wavelength of 390-400 nm.

[0030] The reaction is preferably carried out under the protection of an inert gas, and the inert gas is preferably Ar.

[0031] The mechanism of action of the present invention is as follows:

[0032] The present invention introduces a novel visible light-nickel synergistic catalytic reaction system. Under the synergistic action of visible light redox and nickel catalysis, tetraaryl borate is used as a deoxygenation agent for alcohol to generate neutral diphenylboron radicals, which activate the alcohol to directly break its high bond energy C(sp 3)-O bond, generating an alkyl radical, which is then catalyzed by nickel in a cyclic reductive coupling reaction with an aryl bromide. This system has good substrate universality. Electron-donating aryl bromides are generally suitable, and electron-withdrawing aryl bromides (such as -COOMe) are also applicable to the current system. Small molecule alcohols (such as ethanol, isopropanol, etc.) can also undergo arylation reactions under this system. Different cyclic alcohols, polyaromatic alcohols, and alcohol substrates containing heteroatoms are also suitable for this system. Natural macromolecular alcohols (such as cholesterol, stigmasterol, ibuprofen derivatives, etc.) can also be arylated, and the above substrates can achieve medium or above yields.

[0033] The beneficial effects of the present invention are as follows:

[0034] (1) The present invention uses alcohol as a substrate to carry out a deoxy arylation reaction, and the corresponding arylation product can be directly obtained without pretreatment to prepare an intermediate product.

[0035] (2) The above reduction reaction has good substrate universality and functional group compatibility, high yield, good purity, low reaction cost, and most substrates can give excellent reaction results.

[0036] (3) The deoxyarylation reaction of alcohols is extremely valuable in synthesis and drug molecule modification. The reaction strategy we developed is simple to operate, mild in conditions, and practical. DETAILED DESCRIPTION

[0037] In order to make the technical problems, technical solutions and beneficial effects to be solved by this application more clearly understood, the technical solutions of this application will be further described in detail below in conjunction with specific cases in the embodiments of this application. It should be understood that the specific embodiments described herein are only used to explain this application and are not used to limit the technical solutions of this application. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0038] It should be noted that when a component is referred to as being "fixed to" or "disposed on" another component, it may be located directly or indirectly on the other component. When a component is referred to as being "connected to" another component, it may be directly or indirectly connected to the other component. Terms such as "upper," "lower," "left," "right," "front," "back," "vertical," "horizontal," "top," "bottom," "inside," and "outside" to indicate directions or positions are for ease of description only and are not to be construed as limitations on this technical solution.

[0039] In addition, the terms "first" and "second" are used only for descriptive purposes and should not be understood as indicating or implying relative importance or implicitly specifying the number of technical features. "Multiple" means two or more, unless otherwise specifically defined.

[0040] Example 1

[0041] This example performs a direct deoxygenation arylation reaction of fatty alcohols, and the steps are as follows:

[0042] A magnetic particle of appropriate size was placed in a 25 mL dry Schlenk reaction flask, and Ni(hfacac)2 (9.4 mg, 0.02 mmol, 10 mol%), NaBPh4 (273.8 mg, 0.8 mmol, 4 equiv.), Na2CO3 (10.6 mg, 0.1 mmol, 0.5 equiv.), MS (150 mg) was then replaced with Ar three times to ensure the reaction was carried out under inert gas protection. Subsequently, Cltpy (5.4 mg, 0.02 mmol, 10 mol%), 4-CzIPN (2.4 mg, 0.015 mmol, 1.5 mol%), Ph3N (24.5 mg, 0.4 mmol, 2 equiv.), an alcohol (0.6 mmol, 3 equiv.), and an aryl bromide (0.2 mmol, 1 equiv.) were prepared in dichloroethane (DCE) as the solvent and added sequentially to the reaction flask via syringe. The reaction system was stirred at room temperature for 30 minutes and then placed in a photoreactor cooled by flowing condensed water for 12 hours under 390 nm blue light irradiation. After completion of the reaction, the solvent was removed under reduced pressure, and the desired product was isolated by column chromatography in a 75% yield.

[0043] The reaction is expressed as follows:

[0044]

[0045] Product confirmation: (3,7-dimethyloctyl)benzene

[0046] 1 H NMR(400MHz, CDCl3)δ7.30(t,J=7.5Hz,2H),7.21(d,J=7.6Hz,3H),2.75-2.49(m,2H),1.73-1.60(m,1H),1.5 9-1.42(m,3H),1.39-1.23(m,3H),1.17(dd,J=11.5,3.9Hz,3H),0.95(d,J=6.1Hz,3H),0.90(d,J=6.6Hz,6H).

[0047] 13C NMR (101MHz, CDCl3) δ143.20,128.33,128.23,125.49,39.32,38.99,37.14,33.51,32.51,27.96,24.68,22.71,22.62,19.61.

[0048] Example 2

[0049] The configuration of this example is the same as that of Example 1, except that the structure of the aryl bromide is different, and the yield is 83%.

[0050] The reaction is expressed as follows:

[0051]

[0052] Product confirmation: 4-(3,7-dimethyloctyl)-1,1'-biphenyl

[0053] 1 H NMR (400MHz, CDCl3) δ7.60(d,J=7.0Hz,2H),7.53(d,J=8.3Hz,2H),7.44(t,J =7.7Hz,2H),7.33(t,J=7.4Hz,1H),7.27(d,J=8.1Hz,2H),2.78-2.55(m,2H), 1.67(ddd,J=11.9,7.4,3.0Hz,1H),1.59-1.44(m,3H),1.38-1.26(m,3H),1.1 6(ddd,J=10.4,7.7,6.0Hz,3H),0.96(d,J=6.2Hz,3H),0.89(d,J=6.6Hz,6H).

[0054] 13 C NMR (101MHz, CDCl3) δ142.68,141.49,138.81,129.07,128.99,127.32,127.29, 127.24,39.64,39.28,37.47,33.45,32.87,28.29,25.01,23.03,22.94,19.95.

[0055] Example 3

[0056] This example has the same configuration as Example 1, except that the structure of the aryl bromide is different, and the yield is 70%.

[0057] The reaction is expressed as follows:

[0058]

[0059] Product confirmation: 1-(3,7-dimethyloctyl)-4-methylbenzene

[0060] 1 H NMR (400MHz, CDCl3) δ7.12(s,4H),2.61(dd,J=12.8,5.4Hz,2H),2.36(s,3H),1.67(ddd,J=11.9,7.4,3.0Hz,1H),1. 59-1.44(m,3H),1.38-1.26(m,3H),1.16(ddd,J=10.4,7.7,6.0Hz,3H),0.96(d,J=6.2Hz,3H),0.89(d,J=6.6Hz,6H).

[0061] 13 C NMR (101MHz, CDCl3) δ139.79,134.54,128.61,127.89,39.03,38.83,36.86,32.72,32.19,27.66,24.38,22.40,22.31,20.66,19.31.

[0062] Example 4

[0063] This example has the same configuration as Example 1, except that the structure of the aryl bromide is different, and the yield is 69%.

[0064] The reaction is expressed as follows:

[0065]

[0066] Product confirmation: 1-(tert-butyl)-4-(3,7-dimethyloctyl)benzene

[0067] 1 H NMR (400MHz, CDCl3) δ7.30(d,J=8.2Hz,2H),7.13(d,J=8.0Hz,2H),2.68-2.47(m,2H),1.62-1.56(m,1H),1.55 -1.40(m,3H),1.31(s,9H),1.25-1.18(m,3H),1.16-1.07(m,3H),0.93(d,J=6.3Hz,3H),0.87(d,J=6.6Hz,6H).

[0068] 13C NMR (101MHz, CDCl3) δ148.26,140.14,127.94,125.11,39.29,38.93,37.12,34.30,32.90,32.59,31.40,27.95,24.67,22.71,22.62,19.63.

[0069] Example 5

[0070] This example has the same configuration as Example 1, except that the structure of the aryl bromide is different, and the yield is 72%.

[0071] The reaction is expressed as follows:

[0072]

[0073] Product confirmation: 1-(3,7-dimethyloctyl)-4-phenoxybenzene

[0074] 1 H NMR (400MHz, CDCl3) δ7.35-7.27(m,2H),7.16-7.12(m,2H),7.07(t,J=7.4Hz,1H),7.01-6.96(m,2H),6.94-6.91(m,2H),2.68-2.45(m,2H) ,1.69-1.57(m,1H),1.57-1.42(m,3H),1.32-1.25(m,3H),1.14(tdd,J=8.8,6.1,3.7Hz,3H),0.93(d,J=6.3Hz,3H),0.87(d,J=6.6Hz,6H).

[0075] 13 C NMR (101MHz, CDCl3) δ154.87,138.32,129.69,129.55,122.86,119.06,118 .47,39.37,39.14,37.20,32.82,32.52,28.03,24.75,22.77,22.68,19.68.

[0076] Example 6

[0077] The configuration of this example is the same as that of Example 1, except that the structure of the aryl bromide is different, and the yield is 62%.

[0078] The reaction is expressed as follows:

[0079]

[0080] Product confirmation: tert-butyl(4-(3,7-dimethyloctyl)phenoxy)dimethylsilane

[0081] 1 H NMR (400MHz, CDCl3) δ7.03(d,J=8.4Hz,2H),6.75(d,J=8.4Hz,2H),2.64-2.44(m,2H),1.64-1.56(m,1H),1.54-1.36(m,3H),1 .29(ddt,J=14.2,10.7,5.8Hz,3H),1.18-1.08(m,3H),0.99(s,9H),0.92(d,J=6.2Hz,3H),0.88(d,J=6.6Hz,6H),0.19(s,6H).

[0082] 13 C NMR (101MHz, CDCl3) δ153.69,136.14,129.39,120.04,39.63,39.42,37.47,32.95,32.75,28.28,26.02,25.00,22.93,19.94,18.49,-4.12.

[0083] Example 7

[0084] The configuration of this example is the same as that of Example 1, except that the structure of the aryl bromide is different, and the yield is 71%.

[0085] The reaction is expressed as follows:

[0086]

[0087] Product confirmation: 1-(benzyloxy)-4-(3,7-dimethyloctyl)benzene

[0088] 1H NMR (400MHz, CDCl3) δ7.46(d,J=7.1Hz,2H),7.40(t,J=7.3Hz,3H),7.12(d,J=8.4Hz,2H),6.92(d,J=8.4Hz,2H),5.05(d, J=3.1Hz,2H),2.57(dddd,J=29.7,13.8,10.0,5.7Hz,2H),1.68-1.59(m,1H),1.57-1.38(m,3H),1.35-1.26(m,3H),1.20 -1.11(m,3H),0.93(d,J=6.2Hz,3H),0.89(d,J=6.6Hz,6H).

[0089] 13 C NMR (101MHz, CDCl3) δ156.47,136.94,135.25,128.86,128.20,127.52,127.13,114 .30,69.70,38.99,38.86,36.83,32.24,32.11,27.64,24.36,22.39,22.30,19.29.

[0090] Example 8

[0091] The configuration of this example is the same as that of Example 1, except that the structure of the aryl bromide is different, and the yield is 56%.

[0092] The reaction is expressed as follows:

[0093]

[0094] Product confirmation: 1-(3,7-dimethyloctyl)-4-(trifluoromethoxy)benzene

[0095] 1 H NMR (400MHz, CDCl3) δ7.23(d,J=8.3Hz,2H),7.15(d,J=8.2Hz,2H),2.76-2.54(m,2H),1.70-1.59(m,1H),1.59-1.41 (m,3H),1.31(dddd,J=29.8,16.6,8.9,3.8Hz,3H),1.22-1.11(m,3H),0.97(d,J=6.0Hz,3H),0.91(d,J=6.7Hz,6H).

[0096] 13C NMR (101MHz, CDCl3) δ146.86,141.60,129.18,120.52,38.97,38.55,36.77,32.50,32.12,27.65,24.35,22.37,22.28,19.25.

[0097] 19 F NMR (377 MHz, CDCl3) δ-57.94.

[0098] Example 9

[0099] This example has the same configuration as Example 1, except that the structure of the aryl bromide is different, and the yield is 58%.

[0100] The reaction is expressed as follows:

[0101]

[0102] Product confirmation: (4-(3,7-dimethyloctyl)phenyl)trimethylsilane

[0103] 1 H NMR (400MHz, CDCl3) δ7.44(d,J=7.7Hz,2H),7.18(d,J=7.6Hz,2H),2.65-2.51(m,2H),1.65 1.61(m,1H),1.61-1.48(m,3H),1.35-1.27(m,3H),1.17-1.11(m,3H),0.93(d,J=6.2Hz,3H),0.86(d,J=6.6Hz,6H),0.25(s,9H).

[0104] 13 C NMR (101MHz, CDCl3) δ143.91,136.99,133.34,127.83,39.29,38.86,37.11,33.46,32.57,27.94,24.65,22.69,22.60,19.60,-1.07.

[0105] Example 10

[0106] The configuration of this example is the same as that of Example 1, except that the structure of the aryl bromide is different, and the yield is 67%.

[0107] The reaction is expressed as follows:

[0108]

[0109] Product confirmed: (4-(3,7-dimethyloctyl)phenyl)(methyl)sulfane

[0110] 1 H NMR (400MHz, CDCl3) δ7.20 (dd, J=8.3, 2.7Hz, 2H), 7.11 (dd, J=8.3, 2.7Hz, 2H), 2.66-2.50 (m, 2H), 2.47 (d, J=2.7Hz, 3H), 1.66-1.57 (m, 1H),1.56-1.39(m,3H),1.27(ddt,J=14.5,8.2,3.5Hz,3H),1.17-1.09(m,3H),0.92(dd,J=6.3,2.7Hz,3H),0.87(dd,J=6.7,2.7Hz,6H).

[0111] 13 C NMR (101MHz, CDCl3) δ140.74,135.13,129.21,127.52,39.61,39.24,37.43,33.24,32.74,28.26,24.98,23.01,22.92,19.90,16.75.

[0112] Example 11

[0113] This example has the same configuration as Example 1, except that the structure of the aryl bromide is different, and the yield is 73%.

[0114] The reaction is expressed as follows:

[0115]

[0116] Product confirmed: 2-(4-(3,7-dimethyloctyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

[0117] 1 H NMR (400MHz, CDCl3) δ7.73(d,J=7.9Hz,2H),7.20(d,J=7.7Hz,2H),2.70-2.53(m,2H),1.65-1.58(m,1H),1.53-1 .40(m,3H),1.34(s,12H),1.26(d,J=7.5Hz,3H),1.17-1.09(m,3H),0.91(d,J=6.0Hz,3H),0.86(d,J=6.6Hz,6H).

[0118] 13 C NMR (101MHz, CDCl3) δ146.73,136.29,134.82,127.85,83.59,39.28,38.80,37.10,33.70,32.47,27.93,24.83,24.66,22.69,22.60,19.56.

[0119] Example 12

[0120] This example has the same configuration as Example 1, except that the structure of the aryl bromide is different, and the yield is 58%.

[0121] The reaction is expressed as follows:

[0122]

[0123] Product confirmation: 1-chloro-4-(3,7-dimethyloctyl)benzene

[0124] 1 H NMR (400MHz, CDCl3) δ7.24(d,J=8.4Hz,2H),7.11(d,J=8.4Hz,2H),2.69-2.45(m,2H),1.65-1.57(m,1H) ,1.56-1.37(m,3H),1.32-1.25(m,3H),1.16-1.09(m,3H),0.92(d,J=6.2Hz,3H),0.87(d,J=6.6Hz,6H).

[0125] 13 C NMR (101MHz, CDCl3) δ141.90,131.48,129.99,128.62,39.60,39.16,37.40,33.14,32.70,28.26,24.98,23.01,22.92,19.87.

[0126] Example 13

[0127] This example has the same configuration as Example 1, except that the structure of the aryl bromide is different, and the yield is 61%.

[0128] The reaction is expressed as follows:

[0129]

[0130] Product confirmation: 1-(3,7-dimethyloctyl)-4-(trifluoromethyl)benzene

[0131] 1 H NMR (400MHz, CDCl3) δ7.54(d,J=7.9Hz,2H),7.30(d,J=7.9Hz,2H),2.77-2.58(m,2H),1.69-1.61(m,1H),1 .60-1.39(m,3H),1.36-1.28(m,3H),1.20-1.13(m,3H),0.96(d,J=5.9Hz,3H),0.90(dd,J=6.7,1.6Hz,6H).

[0132] 13 C NMR (101MHz, CDCl3) δ147.33,128.64,125.20,125.16,123.10,39.31,38.70,37.10,33.39,32.49,27.99,24.70,22.69,22.60,19.54.

[0133] 19 F NMR (377 MHz, CDCl3) δ-62.23.

[0134] Example 14

[0135] The configuration of this example is the same as that of Example 1, except that the structure of the aryl bromide is different, and the yield is 43%.

[0136] The reaction is expressed as follows:

[0137]

[0138] Product confirmation: methyl 4-(3,7-dimethyloctyl)benzoate

[0139] 1 H NMR (400MHz, CDCl3) δ7.95(d,J=8.2Hz,2H),7.24(d,J=8.2Hz,2H),3.90(s,3H),2.71-2.59(m,2H),1.62(dd,J=5.1 ,2.6Hz,1H),1.57-1.42(m,3H),1.32-1.24(m,3H),1.16-1.11(m,3H),0.92(d,J=6.2Hz,3H),0.86(d,J=6.6Hz,6H).

[0140] 13C NMR (101MHz, CDCl3) δ167.27,148.88,129.69,128.43,127.59,52.00,39.32,38.62,37.12,33.61,32.52,27.99,24.71,22.74,22.65,19.60.

[0141] Example 15

[0142] This example has the same configuration as Example 1, except that the structure of the aryl bromide is different, and the yield is 69%.

[0143] The reaction is expressed as follows:

[0144]

[0145] Product confirmation: 3-(3,7-dimethyloctyl)-1,1'-biphenyl

[0146] 1 H NMR(400MHz, CDCl3) δ7.60(d,J=7.5Hz,2H),7.46-7.39(m,4H),7.35(dtd,J=8.6,6.0,5.4,2.6Hz,2H),7.18(d,J=8.1Hz,1H),2.76-2 .59(m,2H),1.74-1.63(m,1H),1.54-1.42(m,3H),1.35-1.26(m,3H),1.19-1.11(m,3H),0.95(d,J=4.1Hz,3H),0.87(d,J=6.6Hz,6H).

[0147] 13 C NMR (101MHz, CDCl3) δ143.70,141.46,141.22,128.66,127.32,127.29,127.20,127 .12,124.45,39.31,39.03,37.14,33.60,32.55,27.96,24.69,22.70,22.61,19.63.

[0148] Example 16

[0149] This example has the same configuration as Example 1, except that the structure of the aryl bromide is different, and the yield is 63%.

[0150] The reaction is expressed as follows:

[0151]

[0152] Product confirmation: 1-(3,7-dimethyloctyl)-3-(trifluoromethyl)benzene

[0153] 1 H NMR (400MHz, CDCl3) δ7.43 (s, 2H), 7.37 (d, J = 7.5Hz, 2H), 2.75-2.57 (m, 2H), 1.65-1.58 (m, 1H), 1.55-1.41 ( m,3H),1.31-1.25(m,3H),1.13(ddd,J=11.0,5.5,2.1Hz,3H),0.93(d,J=6.2Hz,3H),0.86(d,J=6.7Hz,6H).

[0154] 13 C NMR (101MHz, CDCl3) δ144.03,131.75,130.66,128.61,125.04,125.01,124.97, 122.48,39.25,38.74,37.04,33.32,32.46,27.94,24.66,22.67,22.59,19.56.

[0155] 19 F NMR (377MHz,CDCl3)δ-62.50.

[0156] Example 17

[0157] The configuration of this embodiment is the same as that of embodiment 1, except that the structure of the aryl bromide is different, and the yield is 80%.

[0158] The reaction is expressed as follows:

[0159]

[0160] Product confirmation: 1-chloro-3-(3,7-dimethyloctyl)benzene

[0161] 1 H NMR (400MHz, CDCl3) δ7.18 (p, J=8.7, 8.1Hz, 3H), 7.06 (d, J=7.3Hz, 1H), 2.70-2.50 (m, 2H), 1.61 (dtd, J=14.1, 7.4, 7. 0,4.1Hz,1H),1.56-1.41(m,3H),1.40-1.19(m,3H),1.19-1.08(m,3H),0.94(d,J=6.1Hz,3H),0.88(d,J=6.7Hz,6H).

[0162] 13 C NMR (101MHz, CDCl3) δ145.30,134.06,129.54,128.55,126.62,125.78,39.37,38.77,37.16,33.29,32.52,28.05,24.75,22.79,22.70,19.65.

[0163] Example 18

[0164] The configuration of this example is the same as that of Example 1, except that the structure of the aryl bromide is different, and the yield is 67%.

[0165] The reaction is expressed as follows:

[0166]

[0167] Product confirmation: 1-(3,7-dimethyloctyl)-3-fluorobenzene

[0168] 1 H NMR (400MHz, CDCl3) δ7.25-7.18(m,1H),6.96(d,J=7.6Hz,1H),6.92-6.83(m,2H),2.61(dddd,J=29.6,13.6,9.9,5.7Hz,2H ),1.70-1.57(m,1H),1.56-1.36(m,3H),1.35-1.20(m,3H),1.19-1.08(m,3H),0.93(d,J=6.1Hz,3H),0.88(d,J=6.7Hz,6H).

[0169] 13 C NMR (101MHz, CDCl3) δ163.80,145.44,129.20,123.64,114.69,111.92,38.97,38.31,36.77,32.93,32.10,27.64,24.35,22.37,22.29,19.24.

[0170] 19 F NMR (377 MHz, CDCl3) δ-114.06.

[0171] Example 19

[0172] This example has the same configuration as Example 1, except that the structure of the aryl bromide is different, and the yield is 61%.

[0173] The reaction is expressed as follows:

[0174]

[0175] Product confirmation: 1-(3,7-dimethyloctyl)-2-fluorobenzene

[0176] 1 H NMR (400MHz, CDCl3) δ7.22-7.11(m,2H),7.08-6.96(m,2H),2.64(ttd,J=19.5,14.1,12.3,5.8Hz,2H),1.68-1.5 6(m,1H),1.56-1.36(m,3H),1.32-1.23(m,3H),1.19-1.07(m,3H),0.94(d,J=6.2Hz,3H),0.87(d,J=6.7Hz,6H).

[0177] 13 C NMR (101MHz, CDCl3) δ162.39,130.57,127.27,123.90,115.28,39.36,37.55,37.11,32.68,28.02,26.66,24.72,22.76,22.68,19.61.

[0178] 19 F NMR (377MHz,CDCl3)δ-119.13.

[0179] Example 20

[0180] This example has the same configuration as Example 1, except that the structure of the aryl bromide is different, and the yield is 72%.

[0181] The reaction is expressed as follows:

[0182]

[0183] Product confirmation: 4-(3,7-dimethyloctyl)-1,2-dimethoxybenzene

[0184] 1H NMR (400MHz, CDCl3) δ6.79(d,J=8.2Hz,1H),6.72(d,J=7.1Hz,2H),3.87(d,J=8.8Hz,6H),2.65-2.46(m,2H),1.66-1.57(m,1H ),1.55-1.36(m,3H),1.31(dtd,J=9.5,5.0,4.5,2.8Hz,3H),1.24-1.11(m,3H),0.93(d,J=6.2Hz,3H),0.87(d,J=6.6Hz,6H).

[0185] 13 C NMR (101MHz, CDCl3) δ148.74,146.94,135.87,120.02,111.69,111.17,55.90, 55.77,39.31,39.15,37.14,33.08,32.47,27.95,24.69,22.69,22.60,19.61.

[0186] Example 21

[0187] This example has the same configuration as Example 1, except that the structure of the aryl bromide is different, and the yield is 69%.

[0188] The reaction is expressed as follows:

[0189]

[0190] Product confirmation: 1-(3,7-dimethyloctyl)-3,5-difluorobenzene

[0191] 1 H NMR (400MHz, CDCl3) δ6.72-6.66(m,2H),6.61(ddd,J=9.1,7.9,2.3Hz,1H),2.69-2.48(m,2H),1.65-1.57(m ,1H),1.56-1.35(m,3H),1.32-1.22(m,3H),1.18-1.09(m,3H),0.92(d,J=6.1Hz,3H),0.87(d,J=6.6Hz,6H).

[0192] 13C NMR (101MHz, CDCl3) δ164.17,161.84,147.17,111.19,110.95,101.02,39.32,38.32,37.10,33.37,32.40,28.01,24.71,22.74,22.66,19.57.

[0193] 19 F NMR (377 MHz, CDCl3) δ-111.04.

[0194] Example 22

[0195] This example has the same configuration as Example 1, except that the structure of the aryl bromide is different, and the yield is 74%.

[0196] The reaction is expressed as follows:

[0197]

[0198] Product confirmation: 3-(3,7-dimethyloctyl)thiophene

[0199] 1 H NMR (400MHz, CDCl3) δ7.29-7.21(m,1H),6.97-6.90(m,2H),2.65-2.46(m,2H),1.66-1.57(m,1H),1.55-1.36( m,3H),1.31(dtd,J=9.5,5.0,4.5,2.8Hz,3H),1.24-1.11(m,3H),0.93(d,J=6.2Hz,3H),0.87(d,J=6.6Hz,6H).

[0200] 13 C NMR (101MHz, CDCl3) δ143.43,128.27,125.04,119.60,39.30,37.80,37.12,32.45,27.96,27.83,24.69,22.70,22.61,19.56.

[0201] Example 23

[0202] The configuration of this example is the same as that of Example 1, except that the structure of the aryl bromide is different, and the yield is 67%.

[0203] The reaction is expressed as follows:

[0204]

[0205] Product confirmation: 2-(3,7-dimethyloctyl)thiophene

[0206] 1 H NMR (400MHz, CDCl3) δ7.10(dd,J=5.1,1.2Hz,1H),6.91(dd,J=5.1,3.4Hz,1H),6.78(dd,J=3.5,1.1Hz,1H),2.91-2.75(m,2H),1.74- 1.65(m,1H),1.57-1.45(m,3H),1.29(ddd,J=12.6,5.8,2.6Hz,3H),1.17-1.12(m,3H),0.92(d,J=6.2Hz,3H),0.86(d,J=6.6Hz,6H).

[0207] 13 C NMR (101MHz, CDCl3) δ146.13,126.61,123.74,122.65,39.27,39.06,37.03,32.29,27.94,27.52,24.66,22.69,22.60,19.48.

[0208] Example 24

[0209] The configuration of this embodiment is the same as that of embodiment 1, except that the structure of the aryl bromide is different, and the yield is 90%.

[0210] The reaction is expressed as follows:

[0211]

[0212] Product confirmation: 4-(3,7-dimethyloctyl)dibenzo[b,d]furan

[0213] 1H NMR (400MHz, CDCl3) δ7.97-7.92(m,1H),7.79(dd,J=5.9,3.1Hz,1H),7.61-7.57(m,1H) ,7.45(ddd,J=8.3,7.3,1.4Hz,1H),7.33(td,J=7.5,1.0Hz,1H),7.28(d,J=6.0Hz,2H),2 .99(qdd,J=13.9,10.0,5.8Hz,2H),1.82(ddt,J=12.8,10.0,5.6Hz,1H),1.67-1.50(m, 3H),1.46-1.29(m,3H),1.22-1.12(m,3H),1.01(d,J=6.4Hz,3H),0.87(d,J=6.6Hz,6H).

[0214] 13 C NMR (101MHz, CDCl3) δ156.07,154.82,127.24,127.14,126.90,124.71,123.81,122.75,122.53, 120.69,118.02,111.72,39.39,37.19,37.13,32.71,28.05,27.48,24.75,22.78,22.69,19.72.

[0215] Example 25

[0216] This example has the same configuration as Example 1, except that the structure of the aryl bromide is different, and the yield is 68%.

[0217] The reaction is expressed as follows:

[0218]

[0219] Product confirmation: 6-(3,7-dimethyloctyl)-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene

[0220] 1H NMR (400MHz, CDCl3) δ7.21(d,J=8.1Hz,1H),7.10(d,J=1.9Hz,1H),6.95(dd,J=8.0,1.9Hz,1H),2.55(dddd,J=37.6,13.9,10.3,5.6Hz,2H),1.67(s,3 H),1.65-1.58(m,1H),1.58-1.43(m,3H),1.43-1.30(m,3H),1.27(d,J=4. 5Hz,13H),1.20-1.05(m,3H),0.93(d,J=6.1Hz,3H),0.87(d,J=6.6Hz,6H).

[0221] 13 C NMR (101MHz, CDCl3) δ144.21,141.57,139.68,125.99,125.90,125.30,39.01,38.50,36.83, 34.91,34.84,33.84,33.59,32.90,32.36,31.60,31.56,27.65,24.40,22.39,22.30,19.35.

[0222] Example 26

[0223] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 54%.

[0224] The reaction is expressed as follows:

[0225]

[0226] Product confirmation: 4-ethyl-1,1'-biphenyl

[0227] 1 H NMR (400MHz, CDCl3) δ7.62-7.59(m,2H),7.56-7.53(m,2H),7.45(t,J=7.6Hz,2H),7. 38-7.33(m,1H),7.30(d,J=7.9Hz,2H),2.72(d,J=7.6Hz,2H),1.31(t,J=7.6Hz,3H).

[0228] 13 C NMR (101MHz, CDCl3) δ143.37,141.17,138.58,128.68,128.27,127.06,126.99,126.94,28.49,15.58.

[0229] Example 27

[0230] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 60%.

[0231] The reaction is expressed as follows:

[0232]

[0233] Product confirmation: 4-(3,3-dimethylbutyl)-1,1'-biphenyl

[0234] 1 H NMR (400MHz, CDCl3) δ7.62-7.59(m,2H),7.56-7.53(m,2H),7.45(t,J=7.6Hz,2H),7. 38-7.33(m,1H),7.30(d,J=7.9Hz,2H),2.64(m,2H),1.56-1.51(m,2H),0.99(s,9H).

[0235] 13 C NMR (101MHz, CDCl3) δ142.75,141.17,138.48,128.71,128.68,127.05,126.99,126.93,46.42,30.87,30.58,29.34.

[0236] Example 28

[0237] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 53%.

[0238] The reaction is expressed as follows:

[0239]

[0240] Product confirmation: 4-(2-cyclopentylethyl)-1,1'-biphenyl

[0241] 1H NMR (400MHz, CDCl3) δ7.62-7.59(m,2H),7.56-7.53(m,2H),7.45(t,J=7.6Hz,2H),7.38-7.33(m,1H),7.30(d,J=7 .9Hz,2H),2.80-2.71(m,2H),1.56(d,J=4.5Hz,2H),0.78-0.68(m,1H),0.49-0.41(m,2H),0.07(d,J=4.9Hz,2H).

[0242] 13 C NMR (101MHz, CDCl3) δ141.82,141.16,138.54,128.86,128.68,126.97,126.9536.70,35.62,10.75,4.52.

[0243] Example 29

[0244] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 55%.

[0245] The reaction is expressed as follows:

[0246]

[0247] Product confirmation: 4-(2-cyclopropylethyl)-1,1'-biphenyl

[0248] 1 H NMR (400MHz, CDCl3) δ7.62-7.59(m,2H),7.56-7.53(m,2H),7.45(t,J=7.6Hz,2H),7.38-7.33(m,1H),7.30(d,J=7 .9Hz,2H),2.70-2.64(m,2H),1.83(dq,J=11.3,5.4,4.5Hz,4H),1.70-1.62(m,4H),1.55(dt,J=12.3,4.8Hz,3H).

[0249] 13 C NMR (101MHz, CDCl3) δ142.23,141.17,138.49,128.76,128.68,127.06,126.98,126.92,39.67,38.12,34.75,32.65,25.22.

[0250] Example 30

[0251] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 55%.

[0252] The reaction is expressed as follows:

[0253]

[0254] Product confirmation: 4-(2-cyclohexylethyl)-1,1'-biphenyl

[0255] 1 H NMR (400MHz, CDCl3) δ7.62-7.59(m,2H),7.56-7.53(m,2H),7.45(t,J=7.6Hz,2H),7.38-7.33(m,1H),7.30(d,J=7.9H z,2H),2.70-2.65(m,2H),1.84-1.78(m,2H),1.71(dq,J=7.5,3.9,2.3Hz,2H),1.59-1.53(m,3H),1.37-1.20(m,6H).

[0256] 13 C NMR (101MHz, CDCl3) δ142.42,141.19,138.47,128.75,128.68,127.06,126.99,126.92,39.39,37.35,33.32,32.87,26.69,26.33.

[0257] Example 31

[0258] This example has the same configuration as Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 69%.

[0259] The reaction is expressed as follows:

[0260]

[0261] Product confirmation: (3r,5r,7r)-1-(2-([1,1'-biphenyl]-4-yl)ethyl)adamantine

[0262] 1H NMR (400MHz, CDCl3) δ7.62-7.59(m,2H),7.56-7.53(m,2H),7.45(t,J=7.6Hz,2H),7.38-7.33(m,1H),7.30(d,J=7.9Hz,2H ),2.65-2.57(m,2H),2.00(d,J=4.8Hz,3H),1.77-1.66(m,6H),1.59(d,J=2.8Hz,6H),1.43(ddd,J=11.4,4.9,2.5Hz,2H).

[0263] 13 C NMR (101MHz, CDCl3) δ143.01,141.21,138.44,128.74,128.67,127.03,126.99,126.91,46.89,42.44,37.25,32.53,29.69,28.77.

[0264] Example 32

[0265] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 70%.

[0266] The reaction is expressed as follows:

[0267]

[0268] Product confirmation: 4-phenethyl-1,1'-biphenyl

[0269] 1 H NMR (400MHz, CDCl3) δ7.60-7.57(m,2H),7.54-7.51(m,2H),7.45-7.41(m,2H ),7.37-7.28(m,3H),7.28-7.26(m,2H),7.22(d,J=7.3Hz,3H),2.96(s,4H).

[0270] 13 C NMR (101MHz, CDCl3) δ141.79,141.11,140.97,138.92,128.93,128.78,128.53,128.43,127.13,127.10,127.06,126.02,37.96,37.63.

[0271] Example 33

[0272] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 70%.

[0273] The reaction is expressed as follows:

[0274]

[0275] Product confirmed: 1-(2-([1,1'-biphenyl]-4-yl)ethyl)naphthalene

[0276] 1 H NMR (400MHz, CDCl3) δ8.14-8.08(m,1H),7.87(dd,J=7.9,1.6Hz,1H),7.73(d,J=8.2Hz,1H),7.62-7.57(m,2H),7.57-7.51(m,3H), 7.49(ddd,J=8.0,6.7,1.4Hz,1H),7.45-7.41(m,2H),7.41-7.36(m,1H),7.36-7.28(m,4H),3.44-3.33(m,2H),3.14-3.03(m,2H).

[0277] 13 C NMR (101MHz, CDCl3) δ141.09,141.06,138.98,137.72,133.90,131.76,128.84,128.72, 127.14,127.05,127.01,126.79,126.02,125.88,125.56,125.48,123.62,36.72,35.06.

[0278] Example 34

[0279] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 49%.

[0280] The reaction is expressed as follows:

[0281]

[0282] Product confirmation: 4-(6-bromohexyl)-1,1'-biphenyl

[0283] 1H NMR (400MHz, CDCl3) δ7.62-7.59(m,2H),7.56-7.53(m,2H),7.45(t,J=7.6Hz,2H),7.38-7.33(m,1H),7.30(d,J=7.9Hz,2H),3.42( t,J=6.8Hz,2H),2.66(t,J=7.7Hz,2H),1.90-1.85(m,2H),1.68(d,J=2.6Hz,2H),1.49(q,J=3.7,1.9Hz,2H),1.39(d,J=5.7Hz,2H).

[0284] 13 C NMR (101MHz, CDCl3) δ141.75,141.16,138.71,128.86,128.76,127.08,127.04,35.48,34.02,32.78,31.29,28.46,28.08.

[0285] Example 35

[0286] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 56%.

[0287] The reaction is expressed as follows:

[0288]

[0289] Product confirmation: 4-(6-chlorohexyl)-1,1'-biphenyl

[0290] 1 H NMR (400MHz, CDCl3) δ7.62-7.59(m,2H),7.56-7.53(m,2H),7.45(t,J=7.6Hz,2H),7.38-7.33(m,1H),7.30(d,J=7.9Hz,2H),3.56(t ,J=6.7Hz,2H),2.68(t,J=7.7Hz,2H),1.83-1.78(m,2H),1.68(d,J=7.7Hz,2H),1.49(dd,J=6.1,3.7Hz,2H),1.41(t,J=6.0Hz,2H).

[0291] 13C NMR (101MHz, CDCl3) δ141.70,141.10,138.63,128.79,128.69,127.01,126.97,45.11,35.42,32.53,31.25,28.52,26.73.

[0292] Example 36

[0293] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 60%.

[0294] The reaction is expressed as follows:

[0295]

[0296] Product confirmed: 4-(2-([1,1'-biphenyl]-4-yl)ethyl)-2,2-dimethyl-1,3-dioxolane

[0297] 1 H NMR (400MHz, CDCl3) δ7.62-7.58(m,2H),7.54(d,J=8.0Hz,2H),7.48-7.42(m,2H),7 .37-7.32(m,1H),7.30(s,2H),4.16(ddd,J=12.9,7.2,5.7Hz,1H),4.06(dd,J=7.9,6 .0Hz,1H),3.57(t,J=7.5Hz,1H),2.83(ddd,J=15.1,9.9,5.6Hz,1H),2.72(ddd,J=13 .9,9.7,6.6Hz,1H),2.06-1.97(m,1H),1.91-1.82(m,1H),1.47(s,3H),1.40(s,3H).

[0298] 13 C NMR (101MHz, CDCl3) δ141.06,140.74,139.02,128.89,128.82,127.25,127.16,127.08,108.88,75.45,69.43,35.40,31.75,27.11,25.84.

[0299] Example 37

[0300] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 59%.

[0301] The reaction is expressed as follows:

[0302]

[0303] Product confirmation: 4-(3-(2-(trifluoromethyl)phenyl)propyl)-1,1'-biphenyl

[0304] 1 H NMR (400MHz, CDCl3) δ7.65-7.58(m,3H),7.57-7.52(m,2H),7.45(dd,J=9.0,7.2Hz,3H),7.34(dt, J=7.5,3.4Hz,2H),7.32-7.27(m,3H),2.91-2.83(m,2H),2.78(t,J=7.8Hz,2H),2.06-1.95(m,2H).

[0305] 13 C NMR (101MHz, CDCl3) δ140.75,140.73,138.46,131.34,130.57,128.46,128.38,126.75,126.68,126.66,125.52,35.19,33.00,32.05.

[0306] Example 38

[0307] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 70%.

[0308] The reaction is expressed as follows:

[0309]

[0310] Product confirmation: 4-(4-phenylbutyl)-1,1'-biphenyl

[0311] 1 H NMR (400MHz, CDCl3) δ7.63 (d, J = 8.1Hz, 2H), 7.58-7.54 (m, 2H), 7.50-7.45 (m, 2H), 7.39-7.35 (m ,1H),7.35-7.27(m,4H),7.23(d,J=7.1Hz,3H),2.76-2.67(m,4H),1.76(dq,J=7.0,3.1Hz,4H).

[0312] 13C NMR (101MHz, CDCl3) δ142.64,141.80,141.24,138.73,128.94,128.81,12 8.53,128.38,127.12,127.09,125.78,77.34,35.93,35.54,31.23,31.17.

[0313] Example 39

[0314] This example has the same configuration as Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 41%.

[0315] The reaction is expressed as follows:

[0316]

[0317] Product confirmation: 4-(6-phenoxyhexyl)-1,1'-biphenyl

[0318] 1 H NMR (400MHz, CDCl3) δ7.62-7.58(m,2H),7.53(d,J=7.9Hz,2H),7.44(t,J=7.6Hz,2H),7.34(t,J=7.7Hz,1H),7.31-7.26(m,4H),6.95-6.90(m, 3H), 3.97 (t, J = 6.5Hz, 2H), 2.68 (t, J = 7.7Hz, 2H), 1.81 (q, J = 7.0Hz, 2H), 1.71 (p, J = 7.5Hz, 2H), 1.57-1.51 (m, 2H), 1.47 (q, J = 6.5, 5.5Hz, 2H).

[0319] 13 C NMR (101MHz, CDCl3) δ158.70,141.51,140.77,138.22,129.06,128.48,128.35,126.66,1 26.64,126.62,120.11,120.07,114.09,67.49,67.37,35.14,31.06,28.87,28.69,25.60.

[0320] Example 40

[0321] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 50%.

[0322] The reaction is expressed as follows:

[0323]

[0324] Product confirmation: 4-(3-(4-fluorophenyl)propyl)-1,1'-biphenyl

[0325] 1 H NMR (400MHz, CDCl3) δ7.61 (dd, J=7.1, 1.5Hz, 2H), 7.56-7.53 (m, 2H), 7.44 (d, J=8.0Hz, 2H), 7.37-7.33 (m, 1H), 7.30(d,J=19.0Hz,2H),7.19-7.12(m,2H),7.06-6.95(m,2H),2.69(dt,J=11.3,7.7Hz,4H),2.03-1.96(m,2H).

[0326] 13 C NMR (101MHz, CDCl3) δ162.52,160.10,141.31,141.14,138.86,137.88,137.85,129.84, 129.76,128.91,128.79,127.15,127.10,127.06,115.21,115.00,35.00,34.67,33.11.

[0327] Example 41

[0328] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 61%.

[0329] The reaction is expressed as follows:

[0330]

[0331] Product confirmation: 4-isopropyl-1,1'-biphenyl

[0332] 1 H NMR (400MHz, CDCl3) δ7.62-7.59(m,2H),7.56-7.53(m,2H),7.45(t,J=7.6Hz,2H),7.38-7.33( m,1H),7.30(d,J=7.9Hz,2H),3.03(ddt,J=11.1,7.0,4.2Hz,1H),1.37(dd,J=6.8,2.7Hz,6H).

[0333] 13C NMR (101MHz, CDCl3) δ147.96,141.16,138.73,128.67,127.05,127.00,126.93,126.83,33.78,24.00.

[0334] Example 42

[0335] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 63%.

[0336] The reaction is expressed as follows:

[0337]

[0338] Product confirmation: 4-cyclopentyl-1,1'-biphenyl

[0339] 1 H NMR (400MHz, CDCl3) δ7.61-7.57(m,2H),7.53(d,J=7.9Hz,2H),7.44(t,J=7.6Hz,2H),7.34(dd,J=7.8,3.4Hz,3H),3.05 (ddd,J=16.7,9.6,7.5Hz,1H),2.12(ddt,J=13.3,8.1,4.8Hz,2H),1.84(ddd,J=7.5,5.0,2.5Hz,2H),1.76-1.60(m,4H).

[0340] 13 C NMR (101MHz, CDCl3) δ145.75,141.24,138.72,128.77,127.61,127.08,127.06,127.02,45.71,34.75,25.61.

[0341] Example 43

[0342] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 72%.

[0343] The reaction is expressed as follows:

[0344]

[0345] Product confirmation: 4-cyclohexyl-1,1'-biphenyl

[0346] 1H NMR (400MHz, CDCl3) δ7.62-7.59(m,2H),7.56-7.53(m,2H),7.45(t,J=7.6Hz,2H),7.38-7.33(m,1H),7.30(d,J=7 .9Hz,2H),2.56(tt,J=11.6,3.5Hz,1H),1.90(ddd,J=22.7,9.8,4.0Hz,4H),1.55-1.46(m,2H),1.46-1.23(m,4H).

[0347] 13 C NMR (101MHz, CDCl3) δ147.29,141.24,138.77,128.72,127.28,127.07,126.97,44.29,34.51,26.96,26.22.

[0348] Example 44

[0349] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 57%.

[0350] The reaction is expressed as follows:

[0351]

[0352] Product confirmation: 4-([1,1'-biphenyl]-4-yl)tetrahydro-2H-pyran

[0353] 1 H NMR (400MHz, CDCl3) δ7.62-7.54(m,4H),7.44(dd,J=8.4,6.9Hz,2H),7.38-7.29(m,3H),4.15 -4.09(m,2H),3.57(td,J=11.5,2.8Hz,2H),2.82(tt,J=11.5,4.5Hz,1H),1.93-1.79(m,4H).

[0354] 13 C NMR (101MHz, CDCl3) δ145.04,141.03,139.37,128.83,127.34,127.25,127.20,127.10,68.49,41.32,34.02.

[0355] Example 45

[0356] The configuration of this embodiment is the same as that of embodiment 1, except that the structures of the aryl bromide and alcohol substrate are different, and the yield is 80%.

[0357] The reaction is expressed as follows:

[0358]

[0359] Product confirmation: 2-([1,1'-biphenyl]-4-yl)-2,3-dihydro-1H-indene

[0360] 1 H NMR (400MHz, CDCl3) δ7.63-7.59(m,2H),7.57(dd,J=8.1,1.7Hz,2H),7.48-7.43(m,2H),7.40(dd,J=8.1,1.7Hz,2H),7.36(td,J=7.3,1 .5Hz,1H),7.30-7.26(m,2H),7.22(dq,J=5.1,2.7,1.6Hz,2H),3.77(p,J=8.6Hz,1H),3.48-3.31(m,2H),3.15(dd,J=15.6,8.9Hz,2H).

[0361] 13 C NMR (101MHz, CDCl3) δ144.63,143.01,141.05,139.23,128.81,127.57,127.26,127.16,127.09,126.55,124.43,45.26,41.01.

[0362] Example 46

[0363] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 74%.

[0364] The reaction is expressed as follows:

[0365]

[0366] Product confirmed: 2-([1,1'-biphenyl]-4-yl)-7-methoxy-1,2,3,4-tetrahydronaphthalene

[0367] 1H NMR (400MHz, CDCl3) δ7.66-7.59(m,3H),7.58(s,1H),7.46(dd,J=8.4,6.8Hz,2H),7.39-7.34(m,3H),7.09(d,J=8.4Hz,1H),6.76(dd,J=8.4,2.7Hz,1H ),6.68(d,J=2.7Hz,1H),3.81(s,3H),3.10-2.96(m,3H),2.93(dd,J=8.0,3 .6Hz,2H),2.19(ddt,J=10.7,4.4,2.0Hz,1H),1.98(tt,J=10.4,1.9Hz,1H).

[0368] 13 C NMR (101MHz, CDCl3) δ157.62,145.80,141.10,139.23,137.75,129.88,128.82,128.48,12 7.39,127.30,127.15,127.11,113.62,112.18,77.31,55.36,40.42,38.03,30.71,28.97.

[0369] Example 47

[0370] The configuration of this example is the same as that of Example 1, except that the structures of the aryl bromide and alcohol substrates are different, and the yield is 50%.

[0371] The reaction is expressed as follows:

[0372]

[0373] Product confirmation: 4-(2-(4-isobutylphenyl)propyl)-1,1'-biphenyl

[0374] 1 H NMR (400MHz, CDCl3) δ7.60-7.57(m,2H),7.50-7.46(m,2H),7.45-7.40(m,2H),7.35-7.30(m,1H),7.17-7.11(m,4H),7.07(d,J=7.8Hz,2H),3 .05-2.95(m,2H),2.79(td,J=10.6,2.9Hz,1H),2.46(d,J=7.2Hz,2H),1.86(dt,J=13.5,6.7Hz,1H),1.28-1.26(m,3H),0.91(d,J=6.5Hz,6H).

[0375] 13 C NMR (101MHz, CDCl3) δ144.24,141.16,140.19,139.38,138.70,129.65,129.0 8,128.75,127.02,126.82,126.77,45.11,44.85,41.47,30.30,22.46,21.18.

[0376] The above-described embodiments merely represent several feasible implementation methods of the present invention. The description thereof is relatively specific and detailed, but it should not be understood as limiting the scope of the invention. The embodiments are not intended to limit the scope of protection in the claims of the present invention. For those skilled in the art, various modifications and improvements can be made without departing from the concept of the present invention. Any equivalent implementation or modification that does not depart from the scope of the present invention should be included in the technology of the present invention.

Claims

1. A method for direct deoxyarylation of fatty alcohols, comprising: directly reacting an alcohol substrate with an aromatic substrate in an organic solvent in the presence of a photocatalyst, a nickel catalyst, a ligand, a base, an additive, a deoxygenation agent, and a molecular sieve under visible light irradiation to obtain the arylated product of the corresponding alcohol; In the formula, R is any one of an alkyl group, a carbocyclic ring, a chain hydrocarbon containing an aromatic structure, a chain hydrocarbon containing a heteroatom, or a carbocyclic ring.

2. The direct deoxyarylation method of a fatty alcohol according to claim 1, wherein: The alkyl group includes unsubstituted C1 to C 30 Alkyl or substituted C1~C 30 The alkyl group of the substituted alkyl group is C6-C 10 Aryl, O-containing heterocycle, OH, OBz, COOEt, COOMe, CF3, OMe, OPh, Ph, OTBS, N, O, S, halogen, or any of CN.

3. The direct deoxyarylation method of a fatty alcohol according to claim 1, wherein: The carbon ring is a 6- to 20-membered carbon ring connected by carbon-carbon bonds.

4. The direct deoxyarylation method of a fatty alcohol according to claim 1, wherein: The alcohol substrate is selected from any one of the following compounds:

5. The direct deoxyarylation method of a fatty alcohol according to claim 1, wherein: The aromatic substrate is selected from any one of the following compounds:

6. The direct deoxyarylation method of a fatty alcohol according to claim 1, characterized in that: The molar concentration of the alcohol substrate in the organic solvent is 0.1 mol / L, and the molar concentration of the aromatic substrate in the organic solvent is 0.03 mol / L.

7. The direct deoxyarylation method of a fatty alcohol according to claim 1, characterized in that: The organic solvent is selected from any one of DCE, DCM, PhCF3, DMF, DMSO, DMAc or a mixed solvent thereof.

8. The direct deoxyarylation method of a fatty alcohol according to claim 1, characterized in that: The photocatalyst is selected from any one of 4-CzIPN, 4-CzPN, 4-CzTPN, 4-DPAIPN, 4-DPAPN, and 4-DPATPN; the nickel catalyst is selected from Ni(hfacac)2, Ni(TMHD)2, Ni(acac)2, Ni(hfacac)2, Any one of NiCl2·glyme, NiCl2·diglyme, NiBr2·diglyme, and NiBr2·glyme.

9. The direct deoxyarylation method of a fatty alcohol according to claim 1, characterized in that: The ligand is a terpyridine ligand, the base is selected from any one of Na2CO3, Li2CO3, Na3PO4, Li3PO4, LiOAc, and NaOAc, the additive is selected from any one of triphenylamine, diphenylamine, 4-methoxytriphenylamine, 4-bromotriphenylamine, 4,4',4"-trimethyltriphenylamine, LiI, and TBAI, the deoxidation agent is a tetraaryl borate, and the molecular sieve is an MS type molecular sieve.

10. The method for direct deoxyarylation of fatty alcohols according to claim 1, wherein: The deoxyarylation reaction is carried out under visible light irradiation, the wavelength of which is a blue light LED of 390-400 nm, the reaction temperature is room temperature, and the reaction time is 4-12 hours.

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