Method for synthesizing benzocyclopentathiophene compound

Abstract

The invention discloses a method for synthesizing benzocyclopentyl thiophene compounds, and belongs to the technical field of organic synthesis. The novel method for constructing 3H-benzo [b] cyclopenta [d] thiophene is developed by utilizing the cycloaddition reaction of propargyl alcohol and benzothiophene boric acid under the catalysis of a double-selenium catalyst Ch-3 reagent, 21 3H-benzo [b] cyclopenta [d] thiophene compounds are successfully synthesized, and the highest yield reaches 96%. The method avoids using a metal catalyst, an electrochemical device and a strong oxidant, and is simple and convenient to operate, mild in reaction condition and good in atom economy. The double-selenium catalyst Ch-3 has the characteristics of low volatility, excellent chemical stability and the like, the reaction safety can be remarkably improved, and a new research direction is opened up for large-scale preparation of heterocyclic compounds.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, and particularly relates to a method for synthesizing benzocyclopentathienyl compounds. BACKGROUND

[0002] Thiophene compounds constitute a core class of heterocyclic compounds, which are widely used in the field of chemistry and exhibit diverse pharmacological activities. Such compounds have a low toxicity and high medicinal potential, and thus occupy an important position in the field of drug research and development. In medicinal chemistry, substituted thiophene derivatives have been used as basic units for constructing key pharmacophores. In the development of anticancer drugs, the focus is on synthesizing new compounds that can specifically act on malignant cells. Notably, some key structural units, such as substituted and heterocyclic modified thiophene skeletons, are present in a variety of pharmacologically active drugs approved by the US FDA, including the antidepressant duloxetine, the antihypertensive drug eprosartan, and the drug for treating schizophrenia olanzapine.

[0003] In addition, clopidogrel and ticlopidine are also used as anti-platelet drugs. Suprofen is used as an anti-inflammatory drug, ritonavir is a potent antiviral drug, and rosiglitazone is a drug used clinically to treat diabetes; many commonly used active antiepileptic drugs (AEDs), including brotizolam, etizolam and tiagabine, contain thiophene skeletons in their structures; when considering antibacterial activity, we found that thiophene derivatives are an important part of the structures of various antibiotics (such as ticarcillin, cefoxitin, temocillin and cefalonium) and antifungal drugs (such as terconazole and sertaconazole); some thiophene derivatives are also used to treat osteoporosis and act as estrogen receptor modulators.

[0004] Many reports indicate that benzo[b]thiophene derivatives can be used to reduce the risk of lung cancer in postmenopausal women, and it is well known that some thiophene-based hybrids, such as 2,6-bis(thiophen-3-ylmethylene)cyclohexanone and thiophenyl Schiff bases, have significantly enhanced free radical scavenging properties and exhibit a wide range of application potential; in addition, some thiophene-containing skeletons are undergoing clinical research, and the advantages of the thiophene heterocyclic core have prompted us to create many new thiophene derivatives in the current work, and we will test the potential properties of these derivatives next.

[0005] The literature analysis and other information data so far show that thiophene and its derivatives are an important class of compounds in the field of medicine, which have various therapeutic potentials, such as anti-malaria, anti-bacterial, anti-fungal, anti-depression, anti-convulsant, anti-viral, anti-cancer, anti-hypertensive, anti-inflammatory and anti-oxidation, and thiophene derivatives can be a rich source of potential entities for searching new generation of bioactive compounds, and it is worth exploring the possibility of this field by fusing different substituted molecules, and possibly discovering compounds with more optimal pharmacological activity. Therefore, it is necessary to continue to explore more modifications to thiophene molecules.

[0006] The traditional preparation process of benzocyclopentathienyl skeleton has significant limitations. Literature research shows that the existing methods generally have the following defects: (1) the synthetic route is long and has low atom economy, and often needs multi-step protection / deprotection operation; (2) relies on noble metal catalytic system or extreme reaction conditions (such as high temperature and high pressure); (3) the substrate pre-functionalization step is complicated, resulting in high synthesis cost. It is worth noting that there is no report on the construction of such heterocyclic system based on selenium Lewis acid catalysis. This study realizes the efficient synthesis of benzocyclopentathienyl under mild conditions for the first time. SUMMARY

[0007] In order to solve the problems existing in the synthesis process of the existing benzocyclopentathienyl compounds, the present application provides a method for synthesizing benzocyclopentathienyl compounds, which is specifically as follows: α-phenyl-α-(2-phenylacetylene) benzyl alcohol compound, benz[b] thiophene-2-boric acid and diselenium catalyst Ch-3 are added to dichloromethane solution, and the reaction is continuously stirred under heating condition. After the reaction is completed, the reaction system is extracted with ethyl acetate, and the organic layers are combined. The organic layer is washed with saturated sodium chloride solution and dehydrated with anhydrous magnesium sulfate to obtain a concentrated organic layer. The concentrated organic layer is subjected to silica gel column chromatography to obtain a benzocyclopentathienyl derivative.

[0008] Preferably, the molar ratio of α-phenyl-α-(2-phenylacetylene) benzyl alcohol compound to benz[b] thiophene-2-boric acid is 1:1.2-1:3, and the molar volume ratio of α-phenyl-α-(2-phenylacetylene) benzyl alcohol compound to dichloromethane is 1:5-1:20, in units of: mol:mL.

[0009] Preferably, the added molar mass percentage of diselenium catalyst Ch-3 is 10%-30% of the molar mass of α-phenyl-α-(2-phenylacetylene) benzyl alcohol compound.

[0010] Preferably, the structure general formula of the α-phenyl-α-(2-phenylacetylene) benzyl alcohol compound is as shown in formula I:

[0011]

[0012] wherein, R1 R 2 R 3 R can be one or more of halogen, alkyl, aryl, cyano or alkoxy.

[0013] Preferably, the benz[b]thiophene-2-boronic acid has a general structure as shown in Formula II:

[0014]

[0015] Preferably, the synthesis method of the diselenide catalyst Ch-3 is as follows: under an argon environment, anhydrous dichloromethane and phenyl selenyl chloride are mixed and stirred to obtain a red solution, gallium chloride is continuously added and the reaction is continuously stirred, then 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene is added, and after the solution color is observed to be lightened to colorless, vacuum distillation is performed, the volume is reduced to saturation, then the positive hexane antisolvent is gradiently injected into the system, a white precipitate is obtained at room temperature, filtration and washing with anhydrous ether are performed, and a white solid is obtained, which is the diselenide catalyst Ch-3.

[0016]

[0017] Preferably, the molar volume ratio of phenyl selenyl chloride to dry dichloromethane is 1:5-1:10, mmol:mL; the molar ratio of gallium chloride to phenyl selenyl chloride is 2:1-1:1; the molar ratio of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene to phenyl selenyl chloride is 1:2-1:1; the volume ratio of n-hexane to dichloromethane is 1:1-2:1, and the addition rate of n-hexane is 1.0 mL / min-3.0 mL / min.

[0018] Preferably, the vacuum distillation condition is 20℃-35℃ under negative pressure.

[0019] Preferably, the heating temperature is 30℃-60℃, and the reaction time is 24 hours-72 hours.

[0020] Preferably, the eluent of the silica gel column chromatography is pure petroleum ether.

[0021] Preferably, the silica gel column used is 200-300 mesh.

[0022] The technical solution provided by the present application can include the following beneficial effects:

[0023] (1) Non-metallic catalytic system, green and efficient: avoid the dependence on noble metals, for the first time, selenium phosphine Lewis acid catalyst is used, without palladium, copper and other metals, to reduce the cost and toxicity from the source.

[0024] (2) Excellent atom economy: the fused ring skeleton is constructed by one step of cycloaddition reaction, avoiding multi-step functional group operation, and the separation yield of target product is as high as 63%~96%, which is significantly better than the similar reactions reported in the literature (usually 40%~70%).

[0025] (3) Mild reaction conditions and simple operation: low temperature and short process: the reaction is carried out at 35℃ under normal pressure, without the need for high temperature, high pressure or special equipment (such as electrochemical device), which simplifies the operation process.

[0026] (4) High stability of catalyst: the diselenium catalyst Ch-3 has low volatility and chemical stability, and is suitable for preparation on a gram scale.

[0027] (5) Wide substrate applicability: compatible with various substituents: good compatibility is shown for electron-donating groups (such as methyl, methoxy) on aryl groups, electron-withdrawing groups (such as halogen, cyano) and large steric groups (such as fluorenyl, phenoxy).

[0028] (6) 21 kinds of different substituted propargyl alcohols and benzothiophene boronic acid can be efficiently reacted, which proves that this method is suitable for late-stage modification of complex molecules.

[0029] (7) Unique catalytic mechanism: the formation of double transition state through Se-O coordination promotes the directional nucleophilic attack of benzothiophene boronic acid on alkyne, avoiding free radical side reactions (TEMPO verification experiment excludes free radical path).

[0030] (8) Safety advantage: low volatility of catalyst reduces the risk of operation, and the reaction does not require strong oxidizing agent or flammable and explosive reagent, which significantly improves the feasibility of industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 is the nuclear magnetic hydrogen spectrum of the white solid prepared in Example 22.

[0032] Figure 2 is the nuclear magnetic carbon spectrum of the white solid prepared in Example 22. DETAILED DESCRIPTION

[0033] The application will be further described in detail below in combination with the drawings and specific examples, but the scope of protection of the application is not limited to the content described.

[0034] The raw materials used in the examples can be purchased through conventional commercial channels, and the synthesis method of the raw materials that cannot be purchased is conventional for those skilled in the art, and the specific synthesis steps can also be found on sciencefinder.

[0035] Example 1

[0036] The preparation of the diselenide catalyst Ch-3 was carried out according to the following procedure:

[0037] Anhydrous dichloromethane (DCM) (10.0 mL) was added to a reaction flask containing phenylselenyl chloride 2-2 (383.04 mg, 2.0 mmol) under argon atmosphere and stirred for 10 minutes to obtain a red solution; then gallium chloride 2-4 (352.16 mg, 2.0 mmol) was added and mixed thoroughly to obtain a reaction mixture, which was stirred at 0 °C for half an hour, then 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene 2-3 (XantPhos) (578.62 mg, 1.0 mmol) was added, and the solution color was observed to be lighter to colorless after 1 hour, the reaction mixture was distilled under reduced pressure at 30 °C water bath temperature and negative pressure until the volume was reduced to about 3.0 mL (close to saturation state), then n-hexane antisolvent (total amount 10.0 mL) was injected into the system at a rate of 1.0 mL / min, and a white precipitate was obtained at room temperature. Filtration and washing with anhydrous diethyl ether yielded white solid catalyst 994.84 mg with a yield of 86%.

[0038]

[0039] Example 2

[0040]

[0041] 1,1-bis(4-fluorophenyl)-3-phenylprop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.12 mmol), and diselenide catalyst Ch-3 (added amount was 20.0% of the molar amount of 1,1-bis(4-fluorophenyl)-3-phenylprop-2-yn-1-ol) were added to a dichloromethane (1 mL) solution, and the reaction mixture was continuously stirred at 40 °C for 30 hours. After the reaction was completed, the reaction system was extracted with ethyl acetate, and the combined organic layer was washed with saturated sodium chloride solution 3 times and dehydrated with anhydrous magnesium sulfate to obtain a concentrated organic layer. The concentrated organic layer was further purified by silica gel column chromatography (200-300 mesh, eluent was pure petroleum ether) to obtain white solid 3,3-bis(4-fluorophenyl)-1-phenyl-3H-benzo[b]cyclopenta[d]thiophene.

[0042] The identification data of the white solid are as follows:

[0043] 1H NMR(400MHz,Chloroform-d)δ7.65(dd,J=19.1,7.8Hz,2H),7.53(d,J=7.4Hz,2H),7.34(t,J=7.3 Hz, 2H), 7.29 (d, J = 7.1Hz, 1H), 7.16 (dd, J = 15.4, 10.1Hz, 6H), 6.84 (t, J = 8.5Hz, 4H), 6.66 (s, 1H).

[0044] 13 C NMR (100MHz, CDCl3) δ163.3, 160.8, 154.0, 145.8, 143.2, 141.6, 139.9, 138.5 (d, J = 3Hz), 135.5, 132 .7,129.4(d,J=8Hz),128.6,128.3,128.2,124.6,123.9(d,J=10Hz),123.0,115.6(d,J=22Hz),64.0.

[0045] HRMS(ESI + ):calcd for C 29 H 18 F2S[M+H] + 437.1170; found 437.1168.

[0046] Example 3

[0047]

[0048] 3-Phenyl-1,1-di-p-tolylprop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.12 mmol), and diselenide catalyst Ch-3 (the amount added is 20.0% of the molar amount of 3-phenyl-1,1-di-p-tolylprop-2-yn-1-ol) are added to a dichloromethane (1 mL) solution, and the reaction mixture is stirred at 40° C. for 30 hours. After the reaction, the reaction system is extracted with ethyl acetate, and the combined organic layers are washed three times with a saturated sodium chloride solution and dehydrated with anhydrous magnesium sulfate to obtain a concentrated organic layer. The concentrated organic layer is further eluted by silica gel column chromatography (200-300 mesh, eluent: pure petroleum ether) to obtain 1-phenyl-3,3-di-p-tolyl-3H-benzo[b]cyclopenta[d]thiophene as a white solid.

[0049] The identification data of the white solid are as follows:

[0050] 1H NMR (400 MHz, Chloroform-d) δ 7.71-7.66 (m, 1H), 7.65-7.61 (m, 1H), 7.58-7.53 (m, 2H), 7.34 (t, J = 7.3 Hz, 2H), 7.29 (s, 1H), 7.15 (d, J = 8.1 Hz, 6H), 6.98 (d, J = 7.7 Hz, 4H), 6.73 (s, 1H), 2.19 (s, 6H).

[0051] 13 C NMR (100 MHz, CDC13) δ 154.6, 145.9, 143.8, 141.1, 140.1, 139.8, 136.8, 136.0, 132.9, 131.8, 129.4, 128.5, 128.3, 128.0, 127.8, 124.4, 123.8, 123.6, 122.9, 64.7, 21.2.

[0052] HRMS (ESI + ): calcd for C 31 H 24 S[M+H] + 429.1671; found 429.1668.

[0053] Example 4

[0054]

[0055] Example 4 1-(4-Fluorophenyl)-1,3-diphenylprop-2-yn-1-ol (0.1 mmol), benz[b]thiophene-2-boronic acid (0.16 mmol), diselenium catalyst Ch-3 (added amount of 15.0% of 1-(4-fluorophenyl)-1,3-diphenylprop-2-yn-1-ol molar amount), were added to dichloromethane (1 mL), the reaction mixture was continuously stirred at 40 °C for 40 h, after the reaction was completed, the reaction system was extracted with ethyl acetate, the combined organic layer was washed with saturated sodium chloride solution for 3 times, and then treated with anhydrous magnesium sulfate to obtain concentrated organic layer, the concentrated organic layer was further purified by silica gel column chromatography (200-300 mesh, eluent was pure petroleum ether) to obtain yellow solid 3-(4-fluorophenyl)-1,3-diphenyl-3H-benzo[b]cyclopenta[d]thiophene.

[0056] The identification data of the yellow solid are as follows

[0057] 1H NMR (400 MHz, Chloroform-d) δ 7.89 (dd, J = 7.5, 1.8 Hz, 1H), 7.86-7.82 (m, 1H), 7.75 (d, J = 6.7 Hz, 2H), 7.55 (t, J = 7.3 Hz, 2H), 7.50 (d, J = 7.2 Hz, 1H), 7.45 (d, J = 1.8 Hz, 1H), 7.44 (s, 2H), 7.41-7.40 (m, 1H), 7.39 (s, 1H), 7.37 (s, 1H), 7.36-7.32 (m, 3H), 7.05 (t, J = 8.7 Hz, 2H), 6.92 (s, 1H).

[0058] 13 C NMR (100 MHz, CDC13) δ 163.2, 160.8, 154.2, 145.9, 143.4, 142.7, 141.5, 140.0, 138.8 (d, J = 3 Hz), 135.7, 132.8, 129.5 (d, J = 8 Hz), 128.8, 128.6, 128.2, 127.8, 127.3, 124.5, 123.8, 123.0, 115.5 (d, J = 21 Hz), 64.6.

[0059] HRMS (ESI + ): calcd for C 29 H 19 FS[M+H] + 419.1264; found 419.1267.

[0060] Example 5

[0061]

[0062] To a solution of 1-(4-bromophenyl)-1,3-diphenylprop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.15 mmol), bis-selenium catalyst Ch-3 (added amount of 15.0% of 1-(4-bromophenyl)-1,3-diphenylprop-2-yn-1-ol molar amount) in dichloromethane (1 mL), the reaction mixture was continuously stirred at 40 °C for 30 hours. After the reaction was completed, the reaction system was extracted with ethyl acetate, and the combined organic layer was washed with saturated sodium chloride solution for 3 times, and then treated with anhydrous magnesium sulfate to obtain a concentrated organic layer. The concentrated organic layer was further purified by silica gel column chromatography (200-300 mesh, eluent: pure petroleum ether) to obtain 3-(4-bromophenyl)-1,3-diphenyl-3H-benzo[b]cyclopenta[d]thiophene as a yellow liquid.

[0063] The identification data for the yellow liquid are as follows:

[0064] 1 H NMR (400 MHz, Chloroform-d) δ 7.81 - 7.77 (m, 1H), 7.75 - 7.71 (m, 1H), 7.64 (dd, J = 6.4, 1.7 Hz, 2H), 7.47 - 7.43 (m, 2H), 7.41 (d, J = 1.5 Hz, 1H), 7.38 (d, J = 2.0 Hz, 1H), 7.36 (d, J = 2.0 Hz, 1H), 7.35 - 7.32 (m, 2H), 7.29 - 7.28 (m, 1H), 7.27 (d, J = 1.7 Hz, 1H), 7.26 - 7.23 (m, 3H), 7.21 (d, J = 2.2 Hz, 1H), 7.19 (dd, J = 4.6, 2.4 Hz, 1H), 6.79 (d, J = 2.2 Hz, 1H).

[0065] 13 C NMR (100 MHz, CDC13) δ 153.7, 145.9, 142.9, 142.3, 142.2, 141.8, 140.1, 135.6, 132.7, 131.7, 129.6, 128.8, 128.6, 128.2, 128.2, 127.8, 127.4, 124.5, 123.8, 123.8, 123.0, 121.2, 64.8.

[0066] HRMS (ESI + ): calcd for C 29 H 19 BrS [M + H] + 479.0464; found 479.0462.

[0067] Example 6

[0068]

[0069] To a solution of 1-(4-chlorophenyl)-1,3-diphenylprop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.14 mmol), diselenium catalyst Ch-3 (1-(4-chlorophenyl)-1,3-diphenylprop-2-yn-1-ol 25.0% of the molar amount), dichloromethane (1 mL) was added, the reaction mixture was continuously stirred at 35 °C for 35 h, after the reaction was completed, the reaction system was extracted with ethyl acetate, the combined organic layer was washed with saturated sodium chloride solution for 3 times, and then treated with anhydrous magnesium sulfate to obtain a concentrated organic layer, which was further purified by silica gel column chromatography (200-300 mesh, eluent: pure petroleum ether) to obtain 3-(4-chlorophenyl)-1,3-diphenyl-3H-benzo[b]cyclopenta[d]thiophene as a light yellow solid.

[0070] The identification data of the light yellow solid are as follows:

[0071] 1 H NMR (400 MHz, Chloroform-d) δ 7.89 (dd, J = 6.1, 2.1 Hz, 1H), 7.84 (dd, J = 6.6, 2.7 Hz, 1H), 7.76-7.72 (m, 2H), 7.55 (t, J = 7.3 Hz, 2H), 7.50 (d, J = 7.3 Hz, 1H), 7.44 (dd, J = 8.2, 1.7 Hz, 2H), 7.35 (tdd, J = 8.7, 6.0, 3.8 Hz, 9H), 6.90 (s, 1H).

[0072] 13 C NMR (100 MHz, CDCl3) δ 153.8, 145.9, 143.0, 142.4, 141.8, 141.7, 140.1, 135.6, 133.0, 132.7, 129.3, 128.8, 128.6, 128.3, 128.2, 127.9, 127.4, 124.6, 123.9, 123.8, 123.0, 64.7.

[0073] HRMS (ESI + ): calcd for C 29 H 19 ClS [M+H] + 435.0969; found 435.0967.

[0074] Example 7

[0075]

[0076] 1-(4-(Benzyloxy)phenyl)-1,3-diphenylprop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.14 mmol), and diselenide catalyst Ch-3 (the amount added is 25.0% of the molar amount of 1-(4-(benzyloxy)phenyl)-1,3-diphenylprop-2-yn-1-ol) were added to a dichloromethane (1 mL) solution. The reaction mixture was stirred at 35° C. for 35 hours. After the reaction, the reaction system was extracted with ethyl acetate. The combined organic layers were washed three times with a saturated sodium chloride solution and dried over anhydrous magnesium sulfate to obtain a concentrated organic layer. The concentrated organic layer was further eluted by silica gel column chromatography (200-300 mesh, eluent: pure petroleum ether) to obtain a yellow liquid 3-(4-(benzyloxy)phenyl)-1,3-diphenyl-3H-benzo[b]cyclopenta[d]thiophene.

[0077] The identification data of the yellow liquid is as follows:

[0078] 1 H NMR(400MHz,Chloroform-d)δ7.71–7.66(m,1H),7.65–7.61(m,1H),7.58–7.53(m,2H),7.34(t,J =7.3Hz,2H),7.29(s,1H),7.15(d,J=8.1Hz,6H),6.98(d,J=7.7Hz,4H),6.73(s,1H),2.19(s,6H).

[0079] 13 C NMR (100MHz, CDCl3) δ157.9,154.5,145.8,143.7,143.1,141.1,139.7,137.0,135.8,135.0,132.8,129.0 ,128.6,128.6,128.5,128.2,128.0,127.8,127.6,127.1,124.4,123.7,123.6,122.9,114.8,70.1,64.6.

[0080] HRMS(ESI + ):calcd for C 36 H 26 OS[M+H] + 507.1783; found 507.1781.

[0081] Example 8

[0082]

[0083] To a solution of 1-(4-phenoxyphenyl)-1,3-diphenylprop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.12 mmol), diselenium catalyst Ch-3 (added 25.0% of 1-(4-phenoxyphenyl)-1,3-diphenylprop-2-yn-1-ol molar amount) in dichloromethane (1 mL), the reaction mixture was stirred at 35 °C for 35 h. After the reaction was completed, the reaction system was extracted with ethyl acetate, and the combined organic layer was washed with saturated sodium chloride solution for 3 times, and then treated with anhydrous magnesium sulfate to obtain a concentrated organic layer. The concentrated organic layer was further purified by silica gel column chromatography (200-300 mesh, eluent: pure petroleum ether) to obtain 3-(4-phenoxyphenyl)-1,3-diphenyl-3H-benzo[b]cyclopenta[d]thiophene as a yellow solid.

[0084] The identification data of the yellow solid are as follows:

[0085] 1 H NMR (400 MHz, Chloroform-d) δ 7.80-7.76 (m, 1H), 7.71-7.67 (m, 1H), 7.62 (d, J = 7.9 Hz, 2H), 7.43 (t, J = 7.5 Hz, 2H), 7.39-7.36 (m, 1H), 7.32 (d, J = 7.2 Hz, 2H), 7.28-7.26 (m, 3H), 7.25 (d, J = 2.9 Hz, 2H), 7.22 (d, J = 3.4 Hz, 2H), 7.21-7.21 (m, 1H), 7.20 (d, J = 1.0 Hz, 1H), 7.04 (d, J = 7.4 Hz, 1H), 6.95 (d, J = 8.0 Hz, 2H), 6.86 (d, J = 8.6 Hz, 2H), 6.80 (s, 1H).

[0086] 13 C NMR (100 MHz, CDCl3) δ 157.0, 156.3, 154.2, 145.8, 143.4, 142.8, 141.2, 139.8, 137.5, 135.7, 132.7, 129.7, 129.2, 128.6, 128.5, 128.2, 128.0, 127.8, 127.1, 124.4, 123.7, 123.6, 123.3, 122.9, 119.0, 118.7, 64.6.

[0087] HRMS (ESI + ): calcd for C 35 H 24 OS[M+H] +493.1621; found 493.1620.

[0088] Example 9

[0089]

[0090] 1-(4-methoxyphenyl)-1,3-diphenylprop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.15 mmol), and diselenide catalyst Ch-3 (the amount added is 20.0% of the molar amount of 1-(4-methoxyphenyl)-1,3-diphenylprop-2-yn-1-ol) were added to a dichloromethane (1 mL) solution. The reaction mixture was stirred at 50° C. for 24 hours. After the reaction, the reaction system was extracted with ethyl acetate. The combined organic layers were washed three times with a saturated sodium chloride solution and dehydrated with anhydrous magnesium sulfate to obtain a concentrated organic layer. The concentrated organic layer was further eluted by silica gel column chromatography (200-300 mesh, eluent: pure petroleum ether) to obtain a yellow liquid 3-(4-methoxyphenyl)-1,3-diphenyl-3H-benzo[b]cyclopenta[d]thiophene.

[0091] The identification data of the yellow liquid is as follows:

[0092] 1 H NMR(400MHz,Chloroform-d)δ7.81(d,J=9.0Hz,1H),7.73(d,J=8.9Hz,1H),7.66(d,J=7.1Hz,2H),7.46(t,J= 7.2Hz,2H),7.41(d,J=7.0Hz,1H),7.34(d,J=7.8Hz,2H),7.31-7.19(m,8H),6.87-6.78(m,3H),3.76(s,3H).

[0093] 13 C NMR (100MHz, CDCl3) δ158.6,154.5,145.8,143.6,143.1,141.0,139.7,135.8,134.7,132.8,12 8.9,128.6,128.4,128.2,128.0,127.8,127.0,124.3,123.7,123.5,122.9,113.9,64.6,55.3.

[0094] HRMS(ESI + ):calcd for C 29 H 20 S[M+H] +431.1464; found431.1464.

[0095] Example 10

[0096]

[0097] 4-(1-Hydroxy-1,3-diphenylprop-2-yn-1-yl)benzonitrile (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.13 mmol), and diselenide catalyst Ch-3 (20.0% of the molar amount of 4-(1-hydroxy-1,3-diphenylprop-2-yn-1-yl)benzonitrile) were added to a dichloromethane (1 mL) solution. The reaction mixture was stirred at 50°C for 29 hours. After the reaction, the reaction system was extracted with ethyl acetate. The combined organic layers were washed three times with a saturated sodium chloride solution and dried over anhydrous magnesium sulfate to obtain a concentrated organic layer. The concentrated organic layer was further eluted using a silica gel column chromatography (200-300 mesh, eluent: pure petroleum ether) to obtain 4-(1,3-diphenyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)benzonitrile as a yellow solid. The identification data of the yellow solid are shown below:

[0098] 1 H NMR(400MHz,Chloroform-d)δ7.77(d,J=8.1Hz,1H),7.51(d,J=8.2Hz,2H),7.48-7.42(m,2H),7.39(d,J=8.1Hz,2H ),7.31(s,1H),7.28(s,1H),7.25(s,4H),7.23(d,J=3.4Hz,2H),7.20(s,1H),7.18(s,1H),7.12(d,J=12.8Hz,2H).

[0099] 13 C NMR (100MHz, CDCl3) δ140.5,139.3,137.0,134.4,134.1,131.4,129.4,127.9,127.8,127.8,12 7.5,127.2,127.1,126.6,125.1,123.6,123.4,122.1,121.9,117.9,110.7,110.0,106.5,28.7.

[0100] HRMS(ESI + ):calcd for C 30 H 19 NS[M+H] + 426.1311; found 426.1307.

[0101] Example 11

[0102]

[0103] To a solution of 1,3-diphenyl-1-(o-tolyl)prop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.12 mmol), diselenium catalyst Ch-3 (added amount of 15.0% of 1,3-diphenyl-1-(o-tolyl)prop-2-yn-1-ol molar amount), dichloromethane (1 mL) was added, the reaction mixture was continuously stirred at 40 °C for 26 hours, after the reaction was completed, the reaction system was extracted with ethyl acetate, the combined organic layer was washed with saturated sodium chloride solution for 3 times, and then treated with anhydrous magnesium sulfate to obtain concentrated organic layer, the concentrated organic layer was further subjected to gradient elution with silica gel column chromatography (200-300 mesh, eluent was pure petroleum ether) to obtain yellow solid 1,3-diphenyl-3-(o-tolyl)-3H-benzo[b]cyclopenta[d]thiophene.

[0104] The identification data of the yellow solid are as follows:

[0105] 1 H NMR (400 MHz, Chloroform-d) δ 7.62 (dd, J = 6.6, 2.7 Hz, 1H), 7.57 (dd, J = 6.6, 2.6 Hz, 1H), 7.51-7.47 (m, 2H), 7.30-7.23 (m, 3H), 7.19 (dd, J = 8.4, 1.6 Hz, 2H), 7.12-7.05 (m, 7H), 6.92 (d, J = 7.9 Hz, 2H), 6.68 (s, 1H), 2.13 (s, 3H).

[0106] 13 C NMR (100 MHz, CDCl3) δ 154.4, 145.9, 143.6, 143.1, 141.2, 139.9, 139.8, 136.8, 135.9, 132.8, 129.4, 128.6, 128.5, 128.2, 128.1, 127.9, 127.8, 127.1, 124.4, 123.7, 123.6, 122.9, 77.3, 65.0, 21.2.

[0107] HRMS (ESI + ): calcd for C 30 H 22 S[M+H] + 415.1515; found 415.1518.

[0108] Example 12

[0109]

[0110] To a solution of 1-(2-fluorophenyl)-1,3-diphenylprop-2-yn-1-ol (0.1 mmol), benz[b]thiophene-2-boronic acid (0.12 mmol), diselenium catalyst Ch-3 (added 15.0% of 1-(2-fluorophenyl)-1,3-diphenylprop-2-yn-1-ol molar amount) in dichloromethane (1 mL), the reaction mixture was stirred at 40 °C for 26 h. After the reaction was completed, the reaction system was extracted with ethyl acetate, and the combined organic layer was washed with saturated sodium chloride solution for 3 times, and then treated with anhydrous magnesium sulfate to obtain a concentrated organic layer. The concentrated organic layer was further purified by silica gel column chromatography (200-300 mesh, eluent: pure petroleum ether) to obtain white solid 3-(2-fluorophenyl)-1,3-diphenyl-3H-benzo[b]cyclopenta[d]thiophene.

[0111] The identification data of the white solid are as follows:

[0112] 1 H NMR (400 MHz, Chloroform-d) δ 7.88-7.83 (m, 1H), 7.77 (q, J = 3.2 Hz, 1H), 7.69 (t, J = 7.7 Hz, 3H), 7.50 (t, J = 7.4 Hz, 2H), 7.44 (d, J = 7.6 Hz, 1H), 7.32-7.28 (m, 2H), 7.26 (d, J = 13.1 Hz, 6H), 7.14-7.06 (m, 2H), 6.97 (s, 1H).

[0113] 13 C NMR (100 MHz, CDCl3) δ 163.2, 160.7, 152.5, 145.8 (d, J = 3 Hz), 142.3, 141.9, 141.4 (d, J = 2 Hz), 140.2, 135.7, 132.6, 129.5, 129.5, 128.7, 128.5, 128.2, 128.1, 127.1, 126.0, 124.4, 124.2 (d, J = 4 Hz), 124.7 (d, J = 8 Hz), 122.9, 116.4 (d, J = 21 Hz), 62.5.

[0114] HRMS (ESI + ): calcd for C 29 H 19 FS[M+H] + 419.1264; found 419.1267.

[0115] Example 13

[0116]

[0117] To a solution of 1,3-diphenyl-1-(m-tolyl)prop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.14 mmol), diselenium catalyst Ch-3 (20.0% of 1,3-diphenyl-1-(m-tolyl)prop-2-yn-1-ol by molar amount) in dichloromethane (1.0 mL), the reaction mixture was stirred at 45 °C for 24 h. After the reaction was completed, the reaction system was extracted with ethyl acetate, and the combined organic layer was washed with saturated sodium chloride solution for 3 times, and then treated with anhydrous magnesium sulfate to obtain a concentrated organic layer. The concentrated organic layer was further purified by silica gel column chromatography (200-300 mesh, eluent: pure petroleum ether) to obtain white solid 1,3-diphenyl-3-(m-tolyl)-3H-benzo[b]cyclopenta[d]thiophene.

[0118] The identification data of the white solid are as follows:

[0119] 1 H NMR (400 MHz, Chloroform-d) δ 7.87-7.83 (m, 1H), 7.82-7.77 (m, 1H), 7.74-7.70 (m, 2H), 7.50 (dd, J = 8.1, 6.5 Hz, 2H), 7.47-7.43 (m, 1H), 7.40 (dd, J = 8.2, 1.5 Hz, 2H), 7.30 (dddt, J = 8.8, 6.8, 4.3, 2.1 Hz, 5H), 7.24 (s, 1H), 7.23-7.19 (m, 2H), 7.10 (t, J = 3.4 Hz, 1H), 6.90 (s, 1H), 2.33 (s, 3H).

[0120] 13 C NMR (100 MHz, CDCl3) δ 154.3, 145.9, 143.6, 143.2, 142.8, 141.3, 139.9, 138.3, 135.9, 132.8, 128.6, 128.5, 128.5, 128.5, 128.3, 128.1, 128.0, 127.9, 127.1, 125.2, 124.4, 123.7, 123.6, 122.9, 65.3, 21.7.

[0121] HRMS (ESI + ): calcd for C 30 H 22S[M+H] + 415.1515; found 415.1512.

[0122] Example 14

[0123]

[0124] To a solution of 1-(2,4-dimethylphenyl)-1,3-diphenylprop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.16 mmol), diselenium catalyst Ch-3 (added 25.0% of 1-(2,4-dimethylphenyl)-1,3-diphenylprop-2-yn-1-ol molar amount) in dichloromethane (1 mL), the reaction mixture was stirred at 60 °C for 27 h. After the reaction was completed, the reaction system was extracted with ethyl acetate, and the combined organic layer was washed with saturated sodium chloride solution for 3 times, and then treated with anhydrous magnesium sulfate to obtain a concentrated organic layer. The concentrated organic layer was further purified by silica gel column chromatography (200-300 mesh, eluent: pure petroleum ether) to obtain 3-(2,4-dimethylphenyl)-1,3-diphenyl-3H-benzo[b]cyclopenta[d]thiophene as a yellow solid.

[0125] The identification data of the yellow solid are as follows:

[0126] 1 H NMR (400 MHz, Chloroform-d) δ 7.73 (d, J = 8.0 Hz, 1H), 7.68 (d, J = 6.7 Hz, 1H), 7.62 (d, J = 8.2 Hz, 2H), 7.40 (t, J = 8.3 Hz, 3H), 7.34 (d, J = 7.8 Hz, 1H), 7.26-7.22 (m, 2H), 7.17 (q, J = 8.3 Hz, 5H), 6.94 (s, 1H), 6.86 (d, J = 2.2 Hz, 2H), 2.24 (s, 3H), 2.01 (s, 3H).

[0127] 13 C NMR (100 MHz, CDCl3) δ 154.7, 145.9, 144.0, 141.9, 141.6, 139.4, 137.7, 137.3, 136.9, 136.0, 133.4, 132.8, 129.0, 128.5, 128.2, 128.0, 127.7, 126.9, 126.7, 126.2, 124.4, 123.7, 123.6, 122.9, 65.8, 21.9, 21.0.

[0128] HRMS (ESI +): calcd for C 31 H 24 S[M+H] + 429.1671 ; found 429.1668.

[0129] Example 15

[0130]

[0131] To a solution of 9-(phenylethynyl)-9H-fluoren-9-ol (0.1 mmol), 2- chlorobenzaldehyde (0.2 mmol), diselenide catalyst Ch-3 (30.0% of the molar amount of 9-(phenylethynyl)-9H-fluoren-9-ol) in dichloromethane (2 mL) was stirred at 60 °C for 72 h. After the reaction was completed, the reaction mixture was extracted with ethyl acetate, and the combined organic layers were washed with saturated sodium chloride solution for 3 times, and dried over anhydrous magnesium sulfate to give a concentrated organic layer. The concentrated organic layer was further purified by silica gel column chromatography (200-300 mesh, eluent: petroleum ether) to give 9-(2-chlorophenyl)-9H-fluoren-9-ol as a yellow solid.

[0132] The identification data of the yellow solid are as follows:

[0133] 1 H NMR (400 MHz, Chloroform-d) δ 7.92 (d, J = 7.3 Hz, 1H), 7.86 (d, J = 7.9 Hz, 2H), 7.81 (d, J = 7.8 Hz, 2H), 7.55 (d, J = 7.3 Hz, 2H), 7.50 (d, J = 7.1 Hz, 1H), 7.45 (d, J = 7.0 Hz, 2H), 7.38 (d, J = 6.6 Hz, 2H), 7.32 (d, J = 7.2 Hz, 1H), 7.26 (d, J = 12.9 Hz, 2H), 7.13 (d, J = 4.6 Hz, 2H), 6.32 (d, J = 2.9 Hz, 1H).

[0134] 13 C NMR (100 MHz, CDC13) δ 150.6, 145.9, 144.2, 144.0, 142.4, 141.8, 139.0, 135.8, 132.7, 128.8, 128.6, 128.3, 128.2, 128.1, 127.9, 124.4, 124.0, 123.9, 123.6, 123.3, 122.6, 120.5, 65.9.

[0135] HRMS (ESI +): calcd for C 29 H 18 S[M+H] + 399.1202; found 399.1203.

[0136] Example 16

[0137]

[0138] Example 16 3-(4-pentylphenyl)-1,1-diphenylprop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.15 mmol), diselenium catalyst Ch-3 (added amount 20.0% of 3-(4-pentylphenyl)-1,1-diphenylprop-2-yn-1-ol molar amount), dichloromethane (1 mL), 60 °C, continuously stirred the reaction mixture for 24 hours, after the reaction was completed, the reaction system was extracted with ethyl acetate, the combined organic layer was washed with saturated sodium chloride solution for 3 times, anhydrous magnesium sulfate was dehydrated to obtain concentrated organic layer, the concentrated organic layer was further eluted by silica gel column chromatography (200-300 mesh, eluent was pure petroleum ether), finally 1-(4-pentylphenyl)-3,3-diphenyl-3H-benzo[b]cyclopenta[d]thiophene was obtained as a light yellow solid.

[0139] The identification data of the light yellow solid are as follows:

[0140] 1 H NMR (400 MHz, Chloroform-d) δ 7.86-7.78 (m, 2H), 7.61 (d, J = 8.0 Hz, 2H), 7.38 (d, J = 6.8 Hz, 4H), 7.31 (s, 2H), 7.29 (s, 3H), 7.28-7.21 (m, 5H), 6.85 (s, 1H), 2.69 (t, J = 7.8 Hz, 2H), 1.69 (q, J = 6.6 Hz, 2H), 1.42-1.34 (m, 4H), 0.93 (d, J = 6.6 Hz, 3H).

[0141] 13 C NMR (100 MHz, CDC13) δ 154.1, 145.9, 143.1, 143.0, 143.0, 141.3, 140.1, 133.1, 132.9, 128.6, 128.5, 128.1, 127.9, 127.1, 124.3, 123.7, 123.6, 123.0, 65.2, 35.9, 31.7, 31.3, 22.7, 14.2.

[0142] HRMS (ESI +): calcd for C 34 H 30 S[M+H] + 471.2146; found 471.2144.

[0143] Example 17

[0144]

[0145] To a solution of 3-(4-(tert-butyl)phenyl)-1,1-diphenylprop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.13 mmol), diselenium catalyst Ch-3 (20.0% of 3-(4-(tert-butyl)phenyl)-1,1-diphenylprop-2-yn-1-ol molar amount) in dichloromethane (1 mL) was added at 60 °C, the reaction mixture was continuously stirred for 24 hours, after the reaction was completed, the reaction system was extracted with ethyl acetate, the combined organic layer was washed with saturated sodium chloride solution for 3 times, and then treated with anhydrous magnesium sulfate to obtain a concentrated organic layer, which was further purified by silica gel column chromatography (200-300 mesh, eluent: pure petroleum ether) to obtain 1-(4-(tert-butyl)phenyl)-3,3-diphenyl-3H-benzo[b]cyclopenta[d]thiophene as a yellow solid.

[0146] The identification data of the yellow solid are as follows:

[0147] 1 H NMR (400 MHz, Chloroform-d) δ 7.81 (t, J = 6.6 Hz, 2H), 7.61 (d, J = 8.3 Hz, 2H), 7.48 (d, J = 8.3 Hz, 2H), 7.34 (d, J = 6.5 Hz, 4H), 7.29-7.19 (m, 8H), 6.83 (s, 1H), 1.38 (s, 9H).

[0148] 13 C NMR (100 MHz, CDCl3) δ 154.2, 151.1, 145.9, 143.2, 143.0, 141.2, 140.0, 132.9, 132.8, 128.6, 127.9, 127.8, 127.1, 125.4, 124.3, 123.7, 123.6, 123.1, 65.1, 34.8, 31.5.

[0149] HRMS (ESI + ): calcd for C 33 H 28 S[M+H] +457.1990; found 457.1988.

[0150] Example 18

[0151]

[0152] To a solution of 3-(4-ethylphenyl)-l,l-diphenylprop-2-yn-l-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.13 mmol), diselenium catalyst Ch-3 (20.0% of 3-(4-ethylphenyl)-l,l-diphenylprop-2-yn-l-ol by molar amount) in dichloromethane (1 mL) was added, the reaction mixture was continuously stirred at 60 °C for 24 hours, after the reaction was completed, the reaction system was extracted with ethyl acetate, the combined organic layer was washed with saturated sodium chloride solution for 3 times, and then treated with anhydrous magnesium sulfate to obtain a concentrated organic layer, which was further purified by silica gel column chromatography (200-300 mesh, eluent: pure petroleum ether) to obtain 1-(4-ethylphenyl)-3,3-diphenyl-3H-benzo[b]cyclopenta[d]thiophene as a yellow liquid.

[0153] The identification data of the yellow liquid are as follows:

[0154] 1 H NMR (400 MHz, Chloroform-d) δ 7.80-7.71 (m, 2H), 7.55 (d, J = 6.4 Hz, 2H), 7.31 (d, J = 8.1 Hz, 4H), 7.28-7.19 (m, 10H), 6.78 (s, 1H), 2.69 (q, J = 7.6 Hz, 2H), 1.26 (t, J = 7.6 Hz, 3H).

[0155] 13 C NMR (100 MHz, CDC13) δ 154.1, 145.8, 144.2, 143.0, 141.3, 140.0, 133.1, 132.8, 128.6, 128.1, 127.9, 127.8, 127.1, 124.3, 123.6, 123.5, 123.0, 65.1, 28.8, 15.6.

[0156] HRMS (ESI + ): calcd for C 31 H 24 S [M+H] + 429.1677; found 429.1675.

[0157] Example 19

[0158]

[0159] To a solution of 1,1-diphenyl-3-(m-tolyl)prop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.15 mmol), diselenium catalyst Ch-3 (10.0% of 1,1-diphenyl-3-(m-tolyl)prop-2-yn-1-ol by molar amount) in dichloromethane (1.5 mL) was added at 40 °C, the reaction mixture was continuously stirred for 26 hours, after the reaction was completed, the reaction system was extracted with ethyl acetate, the combined organic layer was washed with saturated sodium chloride solution for 3 times, and then treated with anhydrous magnesium sulfate to obtain concentrated organic layer, and the concentrated organic layer was further purified by silica gel column chromatography (200-300 mesh, eluent was pure petroleum ether) to obtain yellow solid 3,3-diphenyl-1-(m-tolyl)-3H-benzo[b]cyclopenta[d]thiophene.

[0160] The identification data of the yellow solid are as follows:

[0161] 1 H NMR (400 MHz, Chloroform-d) δ 7.73 (d, J = 7.7 Hz, 1H), 7.33 (d, J = 4.9 Hz, 5H), 7.28-7.19 (m, 9H), 7.14 (d, J = 10.5 Hz, 3H), 6.71 (s, 1H), 2.25 (s, 3H).

[0162] 13 C NMR (100 MHz, CDCl3) δ 153.1, 145.7, 143.6, 143.1, 141.4, 140.3, 136.6, 135.6, 132.9, 130.2, 129.5, 128.7, 128.2, 127.9, 127.2, 125.9, 124.6, 123.7, 123.6, 121.9, 65.7, 20.5.

[0163] HRMS (ESI + ): calcd for C 30 H 22 S[M+H] + 415.1515; found 415.1512.

[0164] Example 20

[0165]

[0166] To a solution of 3-(2-chlorophenyl)-1,1-diphenylprop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.15 mmol), diselenium catalyst Ch-3 (added amount of 25.0% of 3-(2-chlorophenyl)-1,1-diphenylprop-2-yn-1-ol molar amount), dichloromethane (2.0 mL) was added, the reaction mixture was continuously stirred at 50 °C for 30 hours, after the reaction was completed, the reaction system was extracted with ethyl acetate, the combined organic layer was washed with saturated sodium chloride solution for 3 times, and then treated with anhydrous magnesium sulfate to obtain concentrated organic layer, the concentrated organic layer was further purified by silica gel column chromatography (200-300 mesh, eluent was pure petroleum ether) to obtain 1-(2-chlorophenyl)-3,3-diphenyl-3H-benzo[b]cyclopenta[d]thiophene as a light yellow solid.

[0167] The identification data of the light yellow solid are as follows:

[0168] 1 H NMR (400 MHz, Chloroform-d) δ 7.67 (d, J = 8.3 Hz, 1H), 7.42 (d, J = 7.6 Hz, 1H), 7.39-7.31 (m, 2H), 7.28 (d, J = 7.7 Hz, 3H), 7.24 (d, J = 6.6 Hz, 2H), 7.21-7.13 (m, 7H), 7.12-7.07 (m, 2H), 6.78 (s, 1H).

[0169] 13 C NMR (100 MHz, CDCl3) δ 153.1, 145.6, 145.2, 140.7, 137.9, 134.9, 133.6, 132.7, 131.1, 129.8, 129.4, 128.9, 128.7, 128.6, 127.9, 127.2, 126.8, 124.4, 123.7, 123.5, 122.2, 65.8.

[0170] HRMS (ESI + ): calcd for C 29 H 19 ClS [M+H] + 435.0969; found 435.0964.

[0171] Example 21

[0172]

[0173] To a solution of 3-(3-bromophenyl)-1,1-diphenylprop-2-yn-1-ol (0.1 mmol), benzo[b]thiophene-2-boronic acid (0.15 mmol), diselenium catalyst Ch-3 (10.0% of 3-(3-bromophenyl)-1,1-diphenylprop-2-yn-1-ol by molar amount) in dichloromethane (1.5 mL) was added at 40 °C, the reaction mixture was continuously stirred for 26 h. After the reaction was completed, the reaction system was extracted with ethyl acetate, and the combined organic layer was washed with saturated sodium chloride solution for 3 times, and then treated with anhydrous magnesium sulfate to obtain a concentrated organic layer. The concentrated organic layer was further purified by silica gel column chromatography (200-300 mesh, eluent: pure petroleum ether) to obtain 1-(3-bromophenyl)-3,3-diphenyl-3H-benzo[b]cyclopenta[d]thiophene as a yellow liquid.

[0174] The identification data of the yellow liquid are as follows:

[0175] 1 H NMR (400 MHz, Chloroform-d) δ 7.82 (d, J = 2.1 Hz, 2H), 7.70 (d, J = 7.3 Hz, 1H), 7.61 (d, J = 7.6 Hz, 1H), 7.55 (d, J = 7.9 Hz, 1H), 7.35 (d, J = 6.8 Hz, 5H), 7.32-7.24 (m, 8H), 6.89 (s, 1H).

[0176] 13 C NMR (100 MHz, CDCl3) δ 154.4, 145.8, 144.3, 142.6, 140.0, 139.2, 137.9, 132.5, 131.1, 131.0, 130.0, 128.7, 127.8, 127.3, 126.8, 124.6, 123.8, 123.7, 122.6, 65.4.

[0177] HRMS (ESI + ): calcd for C 29 H 19 BrS[M+H] + 479.0464; found 479.0462.

[0178] Example 22

[0179]

[0180] To a solution of 1,1,3-triphenylpropan-2-yn-1-ol (0.2 mmol), benzo[b]thiophene-2-boronic acid (0.24 mmol), diselenium catalyst Ch-3 (added 15% of the molar amount of 1,1,3-triphenylpropan-2-yn-1-ol) in dichloromethane (1.0 mL), the reaction mixture was continuously stirred at 35 °C for 24 h. After the reaction was completed, the reaction system was extracted with ethyl acetate, and the combined organic layers were washed with saturated sodium chloride solution for 3 times, and then treated with anhydrous magnesium sulfate to remove water to obtain a concentrated organic layer. The concentrated organic layer was further purified by silica gel column chromatography (200-300 mesh, eluent: pure petroleum ether) to obtain a white solid product with a separation yield of 87%.

[0181] The identification data of the white solid are as follows:

[0182] 1 H NMR (400 MHz, Chloroform-d) δ 7.83-7.79 (m, 1H), 7.74 (d, J = 7.3 Hz, 1H), 7.69-7.65 (m, 2H), 7.46 (t, J = 7.1 Hz, 2H), 7.41 (d, J = 6.8 Hz, 1H), 7.37 (d, J = 1.4 Hz, 2H), 7.35 (s, 2H), 7.29 (s, 1H), 7.28-7.27 (m, 2H), 7.26-7.22 (m, 5H), 6.86 (d, J = 1.2 Hz, 1H).

[0183] 13 C NMR (101 MHz, Chloroform-d) δ 154.2, 145.9, 143.5, 143.0, 141.4, 139.9, 135.8, 132.8, 128.6, 128.5, 128.2, 128.1, 127.9, 127.1, 124.4, 123.7, 123.6, 122.9, 65.3.

[0184] HRMS (ESI + ): calcd for C 29 H 20 S[M+H] + 401.1358; found 401.1355.

[0185] The white solid product was finally determined to be 1,3,3-triphenyl-3H-benzo[b]cyclopenta[d]thiophene.

[0186] Having described various embodiments of the application, it is to be understood that the above description is meant to be illustrative only and not exhaustive, and is not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art, without departing from the scope and spirit of the described embodiments. The choice of words in this document is intended to best explain the principles of the embodiments, the practical application, or improvement over the technology in the art, or to enable other ordinary skilled in the art to understand the embodiments disclosed herein.

Claims

1. A method for synthesizing benzocyclopenthiophene compounds, characterized in that: An α-phenyl-α-(2-phenylethynyl)benzyl alcohol compound, benzo[b]thiophene-2-boric acid, and a diselenide catalyst Ch-3 are added to a dichloromethane solution, and the reaction is continuously stirred under heating conditions. After the reaction is completed, the reaction system is extracted with ethyl acetate, and the organic layers are combined. The organic layers are washed with a saturated sodium chloride solution and dehydrated with anhydrous magnesium sulfate to obtain a concentrated organic layer. The concentrated organic layer is subjected to silica gel column chromatography to obtain a benzocyclopentathiophene derivative.

2. The method for synthesizing benzocyclopenthiophene compounds according to claim 1, wherein: The molar ratio of the α-phenyl-α-(2-phenylethynyl)benzyl alcohol compound to benzo[b]thiophene-2-boronic acid is 1:1.2 to 1:2, and the molar volume ratio of the α-phenyl-α-(2-phenylethynyl)benzyl alcohol compound to dichloromethane is 1:5 to 1:20, and the unit is: mol:mL.

3. The method for synthesizing benzocyclopenthiophene compounds according to claim 1, wherein: The added molar mass percentage of the diselenide catalyst Ch-3 is 10% to 30% of the molar mass of the α-phenyl-α-(2-phenylethynyl)benzyl alcohol compound.

4. The method for synthesizing benzocyclopenthiophene compounds according to claim 1, wherein: The synthesis method of the diselenide catalyst Ch-3 is as follows: under an argon environment, anhydrous dichloromethane and phenylselenyl chloride are mixed and stirred to obtain a red solution, gallium chloride is continuously added and the reaction is continued with stirring, and then 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene is added. After observing that the color of the solution becomes lighter to colorless, vacuum distillation is performed to reduce the volume to saturation, and then n-hexane antisolvent is gradiently injected into the system to obtain a white precipitate at room temperature. The precipitate is filtered and washed with anhydrous ether to obtain a white solid, which is the diselenide catalyst Ch-3.

5. The method for synthesizing benzocyclopenthiophene compounds according to claim 4, characterized in that: The molar volume ratio of phenylselenochlorido to anhydrous dichloromethane is 1:5 to 1:10, and the unit is mmol:mL; the molar ratio of gallium chloride to phenylselenochlorido is 2:1 to 1:1; the molar ratio of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene to phenylselenochlorido is 1:2 to 1:1; the volume ratio of n-hexane to dichloromethane is 1:1 to 2:1, and the addition rate of n-hexane is 1.0 mL / min to 3.0 mL / min.

6. The method for synthesizing benzocyclopenthiophene compounds according to claim 4, characterized in that: The conditions for reduced pressure distillation are: 20℃~35℃ negative pressure conditions.

7. The method for synthesizing benzocyclopenthiophene compounds according to claim 1, characterized in that: The general structural formula of the α-phenyl-α-(2-phenylethynyl)benzyl alcohol compound is shown in Formula I: Among them, R 1 、R 2 、R 3 It can be one or more of halogen, alkyl, aromatic, cyano or alkoxy.

8. The method for synthesizing benzocyclopenthiophene compounds according to claim 1, wherein: The general structural formula of the benzo[b]thiophene-2-boronic acid is shown in Formula II:

9. The method for synthesizing benzocyclopenthiophene compounds according to claim 1, characterized in that: The heating temperature is 30°C to 60°C, and the reaction time is 24 hours to 72 hours.

10. The method for synthesizing benzocyclopenthiophene compounds according to claim 1, characterized in that: The eluent for silica gel column chromatography was pure petroleum ether, and the silica gel column used was 200-300 mesh.

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