A Silver-Catalyzed Functionalization of 1-Bromoalkynes: Highly Regio-and Stereo-selective Synthesis of (Z)-β-Bromo-1-arylvinyl Aryl Esters

Mingli Sun Jiajun Zhang Yicheng Zhang Pinhua Li Lei Wang

Citation:  Sun Mingli, Zhang Jiajun, Zhang Yicheng, Li Pinhua, Wang Lei. A Silver-Catalyzed Functionalization of 1-Bromoalkynes: Highly Regio-and Stereo-selective Synthesis of (Z)-β-Bromo-1-arylvinyl Aryl Esters[J]. Chinese Journal of Organic Chemistry, 2020, 40(8): 2419-2425. doi: 10.6023/cjoc202003038 shu

银催化1-溴代炔烃的功能化反应:高区域和立体选择性合成(Z)-β-溴-1-芳基乙烯基芳基酯

    通讯作者: 张义成, lbqzhych@163.com
    王磊, leiwang@chnu.edu.cn
  • 基金项目:

    国家自然科学基金 21772062

    国家自然科学基金(No.21772062)资助项目

摘要: 发展一种银催化1-溴代炔烃的官能团反应,用于高度区域和立体选择性合成(Z)-β-溴-1-芳基乙烯基芳基酯.以市售的芳香羧酸为原料,Ag2O为催化剂,以Et3N为碱,1-溴炔烃与芳香羧酸反应,高收率得到相应的(Z)-β-溴-1-芳基乙烯基芳基酯产物.研究结果表明,Ag2O在反应中起着重要的催化作用.

English

  • To develop general and effective methods for the synthesis of complex molecular skeletons is one of the focuses of modern organic chemistry. The haloethylene carboxylates are important intermediates in organic synthesis because the vinyl halide moiety is often employed as the parteners of transition-metal-catalyzed cross-coupling reactions and halogen-metal exchange reactions.[1] Particully, haloethylene carboxylates are frequently used as the important intermediates in the synthetic chemistry and pharmaceutical chemistry.[2-3] For the preparation of haloethylene carboxylates, Barluenga et al.[4] describled a reaction of terminal alkynes with bis(pyridine)iodonium(I) tetrafluoroborate and acetic acid to (E)-β-iodoenol acetates in 1990. Twenty years later, Jiang et al.[5] developed an elegant Ag-catalyzed difunctionalization of terminal alkynes with acetic anhydride and N-halosuccinimide (NXS, X=Cl, Br and I) to (Z)-β-haloenol acetates with high regio- and stereo- selectivity in 2010 (Scheme 1a). Recently, Jiang et al.[6] further reported a Pd-catalyzed sequential nucleophilic addition/oxidative annulation of bromoalkynes with benzoic acids to isocoumarins in one-pot, suggesting via a haloethylene carboxylate intermediate. Although other methods for the preparation of haloethylene carboxylates from terminal alkynes have been reported, [7] there are some drawbacks of poor yields, harsh reaction conditions, complicated procedure or low stereoselectivity to limit the applications. Therefore, to develop efficient method from the com- mercialy available starting materials for the synthesis of halogenated vinyl carboxylic acid esters is highly desired.

    Scheme 1

    Scheme 1.  Transformations of alkynes and 1-bromoalkynes

    During the past decades, haloalkynes have become powerful and highly versatile building blocks in organic chemistry, which exhibit abundant and tunable reactivities, particularly in the presence of transition-metal catalyst.[8] So, the remarkable efforts have been devoted to the synthesis of a valuable scaffold from haloalkynes, and a variety of achievements have been obtained.[9] For examples, a series of nucleophilic additions of fluoride, [10] iodide, [11] acetate, [5, 12] isocyanide, [13] sulfide, [14] and phenol[15] to haloalkynes, have been investigated, providing the corresponding trisubstituted alkenes in exclusive Z-type with high yields. Moreover, several organic transformations using haloalkynes as strating materials under visible light irradiation were estalished, including an alkynylation of α-keto acids with bromoacetylenes to ynones, an oxidative amidation of bromoalkynes with anilines to α-ketoamides, and a three-component cycliza- tion of 2H-azirines, alkynyl bromides and molecular oxygen to oxazoles (Scheme 1b and 1c).[16] However, most of the above reactions are involved in the cleavage of C—X bonds to complete the further transformations. As part of continuing our study on the chemistry of 1-bromoalkynes, we wish to report a silver-catalyzed functionalization 1-bromoalkynes with aryl carboxylic acids to afford (Z)-β-bromo-1-arylvinyl aryl esters in high regio- and stereo-selectivity with good yields under mild reaction conditions (Scheme 1d).

    Initially, a model reaction of phenylethynyl bromide (1a) with benzoic acid (2a) was chosen to optimize reaction conditions. When the model reaction was conducted in the presence of Ag2O (10 mol%) and KOAc (1.5 equiv.) in N, N-dimethylformamide (DMF) under air atmosphere at 80 ℃ for 12 h, a nucleophilic addition of 1a proceeded selectively and delivered the desired product (Z)-2-bromo-1-phenylvinyl benzoate (3a) in 80% yield, and no (E)-isomer of 3a was detected (Table 1, Entry 1). It was found that the base played an important role in the reaction. Screening of the bases indicated that Et3N was the best one for the reaction among the tested inorganic and organic bases, providing 3a in 94% yield (Table 1, Entry 2). Other bases exhibited the less reactivity and showed the following order, Et3N > KOAc > NaOAc > Cs2CO3 > K2CO3 > Na2CO3 > DABCO > K3PO4 > DBU > LiOtBu=KOtBu to the model reaction (Table 1, Entries 3~11). It was noteworthy that the reaction could not occur when LiOtBu and KOtBu were used as bases (Table 1, Entries 10, 11). Then the effect of solvents on the reaction was explored, and the results were also shown in Table 1. When N, N-dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), N-methyl pyrrolidone (NMP), CH3CN, CH3NO2 and 1, 2-dichloroethane (DCE) were used as reaction media, the reactions provided 3a in 27%~78% yields (Table 1, Entries 12~17), indicating the inferior reactivity to the functionalization of 1-bromoalkyne. It should be noted that Ag-catalyst played an important role in the reaction and it was fond that Ag was essential to the reaction (Table 1, Entry 18). The effect of a series of Ag-catalysts on the yield of 3a was explored, and Ag2O showed highest reactivity. Meanwhile, Ag2CO3 and AgOAc used as catalysts, 3a was obtained in 72% and 68% yield, respectively (Table 1, Entries 19, 20). In addition, Ag2SO4 and AgCl used as catalysts gave trace amounts of 3a (Table 1, Entries 21, 22). Finally, the optimal amount of Ag2O and Et3N were found to be 7.5 mol% and 1.2 equiv., respectively for 0.50 mmol scale reaction (Table 1, Entries 23~26).

    Table 1

    Table 1.  Optimization of the reaction conditionsa
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    Entry Solvent Base Ag source Yieldb/%
    1 DMF KOAc Ag2O 80
    2 DMF Et3N Ag2O 94
    3 DMF NaOAc Ag2O 78
    4 DMF Cs2CO3 Ag2O 60
    5 DMF K2CO3 Ag2O 47
    6 DMF Na2CO3 Ag2O 39
    7 DMF DABCO Ag2O 33
    8 DMF K3PO4 Ag2O 23
    9 DMF DBU Ag2O 21
    10 DMF LiOtBu Ag2O NR
    11 DMF KOtBu Ag2O NR
    12 DMA Et3N Ag2O 78
    13 DMSO Et3N Ag2O 56
    14 NMP Et3N Ag 2O 31
    15 CH3CN Et3N Ag2O 28
    16 CH3NO2 Et3N Ag 2O 27
    17 DCE Et3N Ag2O 44
    18 DMF Et3N NR
    19 DMF Et3N Ag2CO3 72
    20 DMF Et3N AgOAc 68
    21 DMF Et3N Ag2SO4 Trace
    22 DMF Et3N AgCl Trace
    23 DMF Et3N Ag2O 94c
    24 DMF Et3N Ag2O 93d
    25 DMF Et3N Ag2O 94e
    26 DMF Et3N Ag2O 92f
    a Reaction conditions: phenylethynyl bromide (1a, 0.50 mmol), benzoic acid (2a, 1.0 mmol), Ag-catalyst (10 mol%), base (0.75 mmol, 1.5 equiv.), solvent (2.0 mL), 80 ℃, sealed tube, air, 12 h. b Isolated yield. c Ag2O (7.5 mol%) was used. d Ag2O (5 mol%) was added. e Et3N (0.60 mmol, 1.2 equiv.) was used. f Et3N (0.50 mmol 1.0 equiv.) was added. NR=No reaction.

    Based on the optimized conditions in our hand, the generality of (Z)-β-bromo-1-phenylvinyl aryl esters prepa- ration from phenylethynyl bromide (1a) was investigated, as shown in Table 2. When aromatic carboxylic acids with an electron-donating group, such as methyl group on the ortho- or meta-position of the benzene rings, the corresponding products (3b and 3c) were obtained in 88% and 84% yields, respectively. It is obvious that the reactions of 1a and substituted benzoic acids with a moderate electron-withdrawing group including Cl, Br, and I on the phenyl rings underwent the nucleophilic addition smoothly to generate the desired products (3d~3i) in 83%~90% yields, neglecting steric effect. It should be noted that halogens such as Cl, Br, and I on the benzoic acid moiety were well tolerated and the obtained products provided further opportunity for organic transformations via C(sp2)X (X=Cl, Br and I) bonds activation and functionalization. When one or two NO2 (nitro group), a strong electron-withdrawing group, was introduced into the benzene rings of aromatic acids, they also reacted with 1a to afford the anticipated products (3j~3l) in 67%~81% yields. The structure of 3j was unambiguously confirmed by X-ray crystallography.[17] The electronic effect and steric effect of the substituted benzonic acids was found to be neglected in the reactions. Moreover, furan-2-carbo- xylic acid and acrylic acid could also be transformed into the corresponding products (3m and3n) in 91% and 72% yields, respectively.

    Table 2

    Table 2.  Scope of aromatic carboxylic acidsa
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    a Reaction conditions: phenylethynyl bromide (1a, 0.50 mmol), aryl carboxylic acid (2, 1.0 mmol), Ag2O (7.5 mol%), Et3N (0.60 mmol, 1.2 equiv.), DMF (2.0 mL), 80 ℃, sealed tube, air, 12 h; isolated yields of the products.

    Subsequently, we turned our attention to extend the scope of acetylene bromides, as shown in Table 3. A number of arylethynyl bromides with an electron- withdrawing or an electron-donating substituent at the para-position of the benzene rings, including F, Cl, Br, Me and n-C3H7, were used to react with benzoic acid (2a) under the standard conditions, affording the according products (3o~3p and 3r~3t) in 88%~91% yields, indicating little electronic effect. On the other hand, meta-substituted phenylethynyl bromide also reacted with 2a smoothly to generate the anticipated product (3q) in 87% yield. In addition, aliphatic terminal acetylene bromide, such as 1-bromoheptyne was used as substrate, and the expected product (3u) was obtained in 69% yield.

    Table 3

    Table 3.  Scope of acetylene bromidesa
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    a Reaction conditions: acetylene bromide (1, 0.50 mmol), benzoic acid (2a, 1.0 mmol), Ag2O (7.5 mol%), Et3N (0.60 mmol, 1.2 equiv.), DMF (2.0 mL), 80 ℃, sealed tube, air, 12 h; isolated yields of the products.

    On the basis of our result and the previous report, [6] a possible mechanism is proposed as shown in Scheme 2. Firstly, Ag2O reacts with Et3N to generate an Ag(I)-com-plex along with the formation of OH. Then, the obtained Ag(NEt3)4-complex undergoes the reaction with phenyl- ethynyl bromide (1a) to afford π-complex A, which is subsequently converted to the corresponding σ-complex C by nucleophilic attack of the benzonic anion (B) from the reaction of benzonic acid (2a) with generated OH. Finally, the silver complex C takes a reaction with Et3N and 2a to provide the desired product (Z)-β-bromo-1- phenylvinyl benzoate (3a) in high regio- and stereo-selectivity, and regeneration of Ag/NEt3-complex and benzonic anion (B) for the next run.

    Scheme 2

    Scheme 2.  Proposed mechanism

    In summary, a silver-catalyzed method for the nucleophilic addition of 1-bromoalkyne with aromatic carboxylic acids to afford (Z)-β-bromo-1-arylvinyl aryl esters has been developed. This reaction uses commercially available aryl acids as nucleophiles and shows a wide range of substrates, which can provide corresponding Z-form addition products in high yields under mild reaction conditions. The reaction has a variety of advantages, including a wide range of substrates, simple operation, easy raw materials, good yields, excellent regio- and stereo-selectivity. A detail mechanistic study is currently underway in our laboratory.

    All reactions were carried out under air. 1H NMR and 13C NMR spectra were measured on a Bruker Avance NMR spectrometer (400 MHz or 100 MHz, respectively) in CDCl3 or DMSO-d6 as solvent with internal tetramethylsilane standard. Ethyl acetate and petroleum ether were used for column chromatography without further purification. All solvents and chemicals were obtained from commercial sources and used as received unless otherwise noted.

    A 10 mL of reaction tube was charged with phenylethynyl bromide (1a, 0.50 mmol), benzoic acid (2a, 1.0 mmol), Ag2O (0.0375 mmol, 7.5 mol%), Et3N (0.60 mmol, 1.2 equiv.), and DMF (2.0 mL). The reaction vessel was placed in an oil bath. After the reaction was carried out at 80 ℃ for 12 h, it was cooled to room temperature, extracted with EtOAc (5.0 mL×3). The organic layers were combined, dried over MgSO4, and concentrated to yield the crude product, which was further purified by flash chromatography (silica gel, petroleum ether/ethyl acetate, V:V=7:1 to 12:1) to give the desired product 3a.

    (Z)-2-Bromo-1-phenylvinyl benzoate (3a):[6] White solid. m.p. 46.1~47.4 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.25 (d, J=8.0 Hz, 2H), 7.70~7.66 (m, 1H), 7.57~7.53 (m, 2H), 7.50~7.49 (m, 2H), 7.37~7.32 (m, 3H), 6.68 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 163.0, 150.6, 133.8, 133.3, 130.3, 129.3, 128.7, 128.7, 128.6, 124.9, 96.6. HRMS (ESI) calcd for C15H12BrO2 [M+H]+ 303.0015, found 303.0018.

    (Z)-2-Bromo-1-phenylvinyl 3-methylbenzoate (3b): White solid. m.p. 54.6~55.9 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.08~8.07 (m, 2H), 7.53~7.49 (m, 3H), 7.46~7.42 (m, 1H), 7.38~7.37 (m, 3H), 6.70 (s, 1H), 2.48 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 163.2, 150.6, 138.5, 134.6, 133.3, 130.7, 129.3, 128.7, 128.6, 128.5, 127.5, 124.9, 96.6, 21.2. HRMS (ESI) calcd for C16H14BrO2 [M+H]+ 317.0172, found 317.0169.

    (Z)-2-Bromo-1-phenylvinyl 2-methylbenzoate (3c): White solid. m.p. 52.8~53.7 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.30 (d, J=7.6 Hz, 2H), 7.53~7.51 (m, 3H), 7.40~7.38 (m, 3H), 7.36~7.35 (m, 2H), 6.69 (s, 1H), 2.70 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 163.5, 150.7, 141.6, 133.5, 132.9, 131.9, 131.3, 129.3, 128.8, 127.7, 125.9, 124.9, 96.6, 21.8. HRMS (ESI) calcd for C16H14BrO2 [M+H]+ 317.0172, found 317.0170.

    (Z)-2-Bromo-1-phenylvinyl 2-chlorobenzoate (3d): White solid. m.p. 62.1~64.2 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.20 (d, J=8.0 Hz, 2H), 7.56~7.54 (m, 2H), 7.54~7.52 (m, 2H), 7.45~7.42 (m, 1H), 7.40~7.39 (m, 3H), 6.69 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 161.5, 150.5, 134.6, 133.4, 133.0, 132.1, 131.4, 129.4, 128.8, 128.3, 126.7, 125.0, 96.8. HRMS (ESI) calcd for C15H11BrClO2 [M+H]+ 336.9625, found 336.9622.

    (Z)-2-Bromo-1-phenylvinyl 4-bromobenzoate (3e): White solid. m.p. 68.9~70.2 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.11 (d, J8.4 Hz, 2H), 7.69 (d, J8.0 Hz, 2H), 7.50~7.48 (m, 2H), 7.38~7.37 (m, 3H), 6.69 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 162.4, 150.5, 133.1, 132.0, 131.7, 129.4, 129.2, 128.8, 127.6, 124.9, 96.8. HRMS (ESI) calcd for C15H11Br2O2 [M+H]+ 382.9100, found 382.9104.

    (Z)-2-Bromo-1-phenylvinyl 2-bromobenzoate (3f): White solid. m.p. 65.6~67.9 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.21~7.19 (m, 2H), 7.77~7.75 (m, 1H), 7.55~7.53 (m, 2H), 7.50~7.43 (m, 2H), 7.40~7.39 (m, 3H), 6.69 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 161.9, 150.5, 134.8, 133.4, 133.0, 132.1, 130.3, 129.4, 128.8, 127.3, 125.0, 122.5, 96.9. HRMS (ESI) calcd for C15H11Br2O2 [M+H]+ 382.9100, found 382.9101.

    (Z)-2-Bromo-1-phenylvinyl 4-iodobenzoate (3g): White solid. m.p. 66.8~68.2 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.11 (d, J=8.8 Hz, 2H), 7.69 (d, J=8.4 Hz, 2H), 7.50~7.48 (m, 2H), 7.38~7.37 (m, 3H), 6.69 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 162.6, 150.4, 138.0, 133.0, 131.6, 129.4, 128.8, 128.1, 124.8, 101.9, 96.8. HRMS (ESI) calcd for C15H11BrIO2 [M+H]+ 428.8982, found 428.8981.

    (Z)-2-Bromo-1-phenylvinyl 3-iodobenzoate (3h): White solid. m.p. 56.6~58.3 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.60 (s, 1H), 8.22 (d, J=7.6 Hz, 1H), 8.00 (d, J=8.0 Hz, 1H), 7.50~7.48 (m, 2H), 7.39~7.38 (m, 3H), 7.31~7.27 (m, 1H), 6.70 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 161.6, 150.4, 142.7, 139.0, 133.0, 130.6, 130.3, 129.5, 129.4, 128.8, 124.9, 96.9, 94.0. HRMS (ESI) calcd for C15H11BrIO2 [M+H]+ 428.8982, found 428.8983.

    (Z)-2-Bromo-1-phenylvinyl 2-iodobenzoate (3i): White solid. m.p. 61.4~62.8 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.24~8.23 (m, 1H), 8.10 (d, J=8.0 Hz, 1H), 7.53~7.50 (m, 3H), 7.40~7.38 (m, 3H), 7.28~7.23 (m, 1H), 6.69 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 162.3, 150.5, 141.9, 133.5, 133.0, 133.0, 131.8, 129.4, 128.8, 128.0, 96.9, 94.9. HRMS (ESI) calcd for C15H11BrIO2 [M+H]+ 428.8982, found 428.8980.

    (Z)-2-Bromo-1-phenylvinyl 4-nitrobenzoate (3j): Pale yellow solid. m.p. 149.1~149.8 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.42 (d, J=8.8 Hz, 2H), 8.37 (d, J=8.8 Hz, 2H), 7.49~7.47 (m, 2H), 7.40~7.38 (m, 3H), 6.71 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 161.2, 150.0, 150.4, 134.0, 132.7, 131.4, 129.6, 128.8, 124.8, 123.7, 97.0. HRMS (ESI) calcd for C15H11BrNO4 [M+H]+ 347.9866, found 347.9866.

    (Z)-2-Bromo-1-phenylvinyl 2-nitrobenzoate (3k): Pale yellow solid. m.p. 146.1~147.4 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.11~8.09 (m, 1H), 7.98~7.96 (m, 1H), 7.78~7.69 (m, 2H), 7.5~7.56 (m, 2H), 7.43~7.41 (m, 3H), 6.67 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 161.3, 150.5, 148.2, 132.9, 132.5, 132.5, 130.4, 129.7, 128.8, 126.1, 125.3, 124.1, 97.1. HRMS (ESI) calcd for C15H11BrNO4 [M+H]+ 347.9866, found 347.9869.

    (Z)-2-Bromo-1-phenylvinyl 3, 5-dinitrobenzoate (3l): Yellow solid. m.p. 157.9~158.3 ℃; 1H NMR (400 MHz, CDCl3) δ: 9.34~9.33 (m, 3H), 7.48~7.47 (m, 2H), 7.42~7.40 (m, 3H), 6.67 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 159.2, 150.2, 148.8, 132.4, 132.2, 129.9, 129.8, 128.9, 124.9, 123.1, 97.4. HRMS (ESI) calcd for C15H10BrN2O6 [M+H]+ 392.9717, found 392.9718.

    (Z)-2-Bromo-1-phenylvinyl furan-2-carboxylate (3m): White solid. m.p. 86.1~87.2 ℃; 1H NMR (400 MHz, CDCl3) δ: 7.70 (s, 1H), 7.49~7.46 (m, 3H), 7.37~7.36 (m, 3H), 6.68 (s, 1H), 6.62~6.61 (m, 1H). 13C NMR (100 MHz, CDCl3) δ: 154.6, 149.8, 147.5, 143.2, 133.0, 129.4, 128.7, 124.9, 120.0, 112.2, 97.1. HRMS (ESI) calcd for C13H10BrO3 [M+H]+ 292.9808, found 292.9811.

    (Z)-2-Bromo-1-phenylvinyl acrylate (3n): Pale yellow oil. 1H NMR (400 MHz, CDCl3) δ: 7.44~7.43 (m, 2H), 7.38~7.36 (m, 3H), 6.70~6.66 (m, 1H), 6.61 (s, 1H), 6.41~6.34 (m, 1H), 6.10~6.07 (m, 1H); 13C NMR (100 MHz, CDCl3) δ: 162.3, 150.2, 133.3, 133.1, 129.3, 128.7, 126.9, 124.8, 96.5. HRMS (ESI) calcd for C11H10BrO2 [M+H]+ 252.9859, found 252.9862.

    (Z)-2-Bromo-1-(p-tolyl)vinyl benzoate (3o): White solid. m.p. 76.2~77.2 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.27 (d, J=8.0 Hz, 2H), 7.70~7.66 (m, 1H), 7.57~7.53 (m, 2H), 7.40 (d, J=8.0 Hz, 2H), 718 (d, J=8.0 Hz, 2H), 6.63 (s, 1H), 2.36 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 163.1, 150.7, 139.5, 133.7, 130.5, 130.3, 129.4, 128.8. 128.6, 124.8, 95.6, 21.2. HRMS (ESI) calcd for C16H14Br- O2 [M+H]+ 317.0172, found 317.0174.

    (Z)-2-Bromo-1-(4-fluorophenyl)vinyl benzoate (3p): White solid. m.p. 79.4~80.9 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.26 (d, J=8.0 Hz, 2H), 7.70~7.67 (m, 1H), 7.57~7.53 (m, 2H), 7.50~7.47 (m, 2H), 7.08~7.04 (m, 2H), 6.62 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 163.2 (d, JCF=250.8 Hz), 163.0, 149.7, 133.9, 130.3, 129.6 (d, JCF=3.2 Hz), 128.6, 128.5, 126.9 (d, JCF=8.4 Hz), 115.8 (d, JCF=21.9 Hz), 96.4 (d, JCF=1.6 Hz). HRMS (ESI) calcd for C15H11BrFO2 [M+H]+ 320.9921, found 320.9925.

    (Z)-2-Bromo-1-(3-fluorophenyl)vinyl benzoate (3q): White solid. m.p. 75.6~76.2 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.06 (d, J=7.6 Hz, 2H), 7.94 (d, J=8.8 Hz, 2H), 7.56~7.49 (m, 3H), 7.42~7.36 (m, 4H), 6.70 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 162.6 (d, JCF=248.2 Hz), 161.9 (d, JCF=3.2 Hz), 150.5, 133.0, 130.8 (d, JCF=7.7 Hz), 130.3 (d, JCF=7.9 Hz), 129.4, 128.8, 126.0 (d, JCF=3.2 Hz), 124.9, 120.1 (d, JCF=21.2 Hz), 117.1 (d, JCF=23.1 Hz), 96.8. HRMS (ESI) calcd for C15H11BrFO2 [M+H]+ 320.9921, found 320.9922.

    (Z)-2-Bromo-1-(4-chlorophenyl)vinyl benzoate (3r): White solid. m.p. 86.3~88.2 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.25 (d, J=8.0 Hz, 2H), 7.70~7.66 (m, 1H), 7.57~7.53 (m, 2H), 7.43 (d, J=8.4 Hz, 2H), 7.34 (d, J=8.0 Hz, 2H), 6.69 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 163.0, 149.7, 135.3, 133.9, 131.8, 130.3, 129.0, 128.7, 128.5, 126.2, 97.3. HRMS (ESI) calcd for C15H11BrClO2 [M+H]+ 336.9625, found 336.9628.

    (Z)-2-Bromo-1-(4-bromophenyl)vinyl benzoate (3s): White solid. m.p. 83.3~84.8 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.24 (d, J=7.6 Hz, 2H), 7.70~7.67 (m, 1H), 7.57~7.53 (m, 2H), 7.49 (d, J=8.0 Hz, 2H), 7.36 (d, J=8.4 Hz, 2H), 6.69 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 163.0, 149.7, 133.9, 132.3, 131.9, 130.3, 128.7, 128.4, 126.4, 123.5, 97.4. HRMS (ESI) calcd for C15H11Br2O2 [M+H]+ 382.9100, found 382.9101.

    (Z)-2-Bromo-1-(4-propylphenyl)vinyl benzoate (3t): White solid. m.p. 98.7~100.3 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.25 (d, J=7.6 Hz, 2H), 7.69~7.66 (m, 1H), 7.56~7.53 (m, 2H), 7.40 (d, J=8.0 Hz, 2H), 7.17 (d, J=8.0 Hz, 2H), 6.63 (s, 1H), 2.59 (t, J=7.6 Hz, 2H), 1.65 (q, J=7.2 Hz, 2H), 0.95 (t, J=7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ: 163.1, 150.6, 144.2, 133.7, 130.7, 130.3, 128.8, 128.8, 28.6, 124.8, 95.6, 37.7, 24.2, 13.6. HRMS (ESI) calcd for C18H18BrO2 [M+H]+ 345.0485, found 345.0487.

    (Z)-1-Bromohept-1-en-2-yl benzoate (3u):[6] pale yellow oil. 1H NMR (400 MHz, CDCl3) δ: 8.17~8.15 (m, 2H), 7.65~7.61 (m, 1H), 7.52~7.48 (m, 2H), 5.94 (s, 1H), 2.44 (t, J=7.6 Hz, 2H), 1.57~1.54 (m, 2H), 1.38~1.32 (m, 4H), 0.92~0.89 (m, 2H); 13C NMR (100 MHz, CDCl3) δ: 163.0, 153.2, 133.5, 130.0, 129.0, 128.5, 93.7, 33.5, 31.0, 25.8, 22.2, 13.8. HRMS (ESI) calcd for C14H18BrO2 [M+H]+ 297.0485, found 297.0486.

    Supporting Information 1H NMR and 13C NMR spectra of compounds 3a~3u. The Supporting Information is available free of charge via the Internet at http://sioc-journal.cn/.


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      The X-ray single crystal structure of (Z)-2-bromo-1-phenylvinyl 4-nitrobenzoate (3j, CCCD: 1990480).

  • Scheme 1  Transformations of alkynes and 1-bromoalkynes

    Scheme 2  Proposed mechanism

    Table 1.  Optimization of the reaction conditionsa

    Entry Solvent Base Ag source Yieldb/%
    1 DMF KOAc Ag2O 80
    2 DMF Et3N Ag2O 94
    3 DMF NaOAc Ag2O 78
    4 DMF Cs2CO3 Ag2O 60
    5 DMF K2CO3 Ag2O 47
    6 DMF Na2CO3 Ag2O 39
    7 DMF DABCO Ag2O 33
    8 DMF K3PO4 Ag2O 23
    9 DMF DBU Ag2O 21
    10 DMF LiOtBu Ag2O NR
    11 DMF KOtBu Ag2O NR
    12 DMA Et3N Ag2O 78
    13 DMSO Et3N Ag2O 56
    14 NMP Et3N Ag 2O 31
    15 CH3CN Et3N Ag2O 28
    16 CH3NO2 Et3N Ag 2O 27
    17 DCE Et3N Ag2O 44
    18 DMF Et3N NR
    19 DMF Et3N Ag2CO3 72
    20 DMF Et3N AgOAc 68
    21 DMF Et3N Ag2SO4 Trace
    22 DMF Et3N AgCl Trace
    23 DMF Et3N Ag2O 94c
    24 DMF Et3N Ag2O 93d
    25 DMF Et3N Ag2O 94e
    26 DMF Et3N Ag2O 92f
    a Reaction conditions: phenylethynyl bromide (1a, 0.50 mmol), benzoic acid (2a, 1.0 mmol), Ag-catalyst (10 mol%), base (0.75 mmol, 1.5 equiv.), solvent (2.0 mL), 80 ℃, sealed tube, air, 12 h. b Isolated yield. c Ag2O (7.5 mol%) was used. d Ag2O (5 mol%) was added. e Et3N (0.60 mmol, 1.2 equiv.) was used. f Et3N (0.50 mmol 1.0 equiv.) was added. NR=No reaction.
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    Table 2.  Scope of aromatic carboxylic acidsa

    a Reaction conditions: phenylethynyl bromide (1a, 0.50 mmol), aryl carboxylic acid (2, 1.0 mmol), Ag2O (7.5 mol%), Et3N (0.60 mmol, 1.2 equiv.), DMF (2.0 mL), 80 ℃, sealed tube, air, 12 h; isolated yields of the products.
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    Table 3.  Scope of acetylene bromidesa

    a Reaction conditions: acetylene bromide (1, 0.50 mmol), benzoic acid (2a, 1.0 mmol), Ag2O (7.5 mol%), Et3N (0.60 mmol, 1.2 equiv.), DMF (2.0 mL), 80 ℃, sealed tube, air, 12 h; isolated yields of the products.
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  • 发布日期:  2020-08-01
  • 收稿日期:  2020-03-15
  • 修回日期:  2020-05-18
  • 网络出版日期:  2020-05-27
通讯作者: 陈斌, bchen63@163.com
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