多烯(polyenes)[1]结构是一类广泛存在于生物化学过程中的结构单元. 这类结构由多个碳-碳双键连接而成, 赋予了分子独特的光物理性质和化学反应性, 使其在生命体系中扮演着不可或缺的角色(Scheme 1a). 例如, 在视觉生理过程中起核心作用的视黄醛(Retinal)、作为维生素A前体的β-胡萝卜素(β-carotene)均是典型的多烯化合物[1b,2]. 此外, 法尼基焦磷酸(farnesyl diphosphate)作为类异戊二烯代谢途径中的关键中间体, 是合成甾醇、萜类等大量天然产物的通用砌块[3], 彰显了多烯在生物合成中的基础性地位. 二十二碳六烯酸(DHA)作为一种重要的长链多不饱和脂肪酸, 则是大脑[4]和视网膜中细胞膜的关键组分, 对神经发育与功能至关重要. 在天然产物领域, 像菲律宾菌素(Filipin)这样的多烯大环内酯类抗生素, 则通过与细胞膜中的甾醇结合而展现出强大的抗真菌活性[5]. 这些例子共同印证了多烯类化合物在从生命基础到高级功能的各个层面所具有的广泛性与重要性.
然而, 与这类结构的重要性形成鲜明对比的是, 多烯在化学合成中, 特别是选择性官能化方面, 面临着严峻的挑战[6]. 多烯骨架中多个电子密度相近的共轭双键具有高度的反应相似性[7], 使得化学家难以精确控制反应的位点[8]. 当亲电试剂或自由基等物种进攻时, 通常会得到1,2-、1,4-甚至1,6-加成等多种反应的混合物, 区域选择性和立体选择性极难控制[9]. 此外, 多烯体系对光、热、氧等条件往往非常敏感, 在反应条件下容易发生聚合、异构化或降解[10], 导致产物复杂、收率低下. 因此, 发展高效、高选择性的方法来实现多烯的定点官能化, 从而能够定向修饰其生物活性、探究其构效关系或合成其类似物, 已成为有机合成化学领域一个长期且富有吸引力的前沿课题[11].
1 结果与讨论
本研究以二氯碘苯(PhICl2)为自由基氯源[14], 在二氯甲烷体系中考察香叶醇衍生物底物1a的光引发氯代反应[15-16] (表1, Entry 1). 初步实验表明, LED光照与无光照条件对反应结果无显著差异, 故后续实验均在避光条件下开展. 当溶剂替换为乙腈时(表1, Entry 2), 四氯代产物(2a-3)消失, 主要生成烯丙基氯产物(2a-4)及少量远端二氯代产物(2a-1), 这与Pronin课题组报道的近端烯烃官能化路径形成鲜明对比. 基于烯丙基氯产物的合成价值, 本研究通过引入碱性添加剂优化体系, 以期提高消除反应的效率(表1, Entries 3~6). 当吡啶用量增至3 equiv.时, 2a-4的产率达88% (表1, Entry 5), 同时二氯代产物降至9%. 值得注意的是, 虽然体系中单独加入相转移催化剂后无明显效果(表1, Entry 7), 但是协同使用相转移催化剂与吡啶可使选择性显著提升, 单一产物2a-4产率达92% (表1, Entry 8). 进一步采用盐酸吡啶盐替代吡啶时, 产率提高至95% (表1, Entry 9); 使用4-溴代吡啶盐酸盐亦取得等同效果(表1, Entry 10). 控制实验证实, 反应体系对氧气不敏感(表1, Entry 11). 值得注意的是, 酯基邻位烯烃的双氯代产物(2a-2)在所有条件下均未监测到, 表明该体系具有显著的区域选择性.
表1 反应条件筛选Table 1 Optimization of reaction conditions |
| Entrya | Base (equiv.) | Additive | Yieldb/% of 2a-1/2a-3/2a-4 |
|---|---|---|---|
| 1c | — | — | 63/13/0 |
| 2d | — | — | 26/0/28 |
| 3 | Pyridine (1.0) | — | 19/0/56 |
| 4 | Pyridine (2.0) | — | 11/0/64 |
| 5 | Pyridine (3.0) | — | 9/0/88 |
| 6 | Pyridine (4.0) | — | 21/0/59 |
| 7 | — | TBABF4 | 42/11/0 |
| 8 | Pyridine (3.0) | TBABF4 | 0/0/92e |
| 9 | Py•HCl (3.0) | TBABF4 | 0/0/95e |
| 10 | 4-Br-Py•HCl (3.0) | TBABF4 | 0/0/96e |
| 11f | 4-Br-Py•HCl (3.0) | TBABF4 | 0/0/96e |
a Reaction conditions: 1a (0.1 mmol, 1.0 equiv.), PhICl2 (0.11 mmol, 1.1 equiv.), 4-bromopyridine hydrochloride (0.3 mmol), TBABF4 (0.3 mmol) in DCM (4 mL) were stirred at r.t. for 1.5 h under N2. b Determined by 1H NMR analysis. c The reaction was irradiated with 380 nm blue LEDs. d The solvent was MeCN. e Yields of isolated products. f The reaction was in open air. |
本研究在优化反应条件后, 系统考察了底物适用范围(表2), 发现苯环上碘原子为邻、间、对位取代以及没有取代基团时, 均能保持高效反应活性(2a~2d, 产率 >90%). 除苯甲酸保护基(2d)外, 体系可兼容烷基羧酸酯(2e和2f)、吡啶羧酸酯(2g)及酰胺(2h)等多种官能团. 进一步研究发现, 通过调控邻近酯基的烯烃取代基(2i~2j), 即使将邻位烯烃改为末端烯烃(2j), 仍可实现远端烯烃的高效高选择性官能化. 该规律在3-甲基巴豆醛衍生物(2k)的双1,1-二甲基取代烯烃体系中同样成立. 研究拓展至复杂分子体系时发现, 苯基乙烯取代(单/二/三取代)的二烯(1n~1p)近端烯烃取代度不影响远端选择性, 而降冰片烯衍生物(1q)的反应验证了体系对刚性环状结构的适用性(2q). 本工作通过底物兼容性的系统性考察, 证实了该体系对官能团多样性、取代位阻差异及复杂分子结构具有优异的兼容性和选择性调控能力.
表2 底物范围考察aTable 2 Investigation of substrate scope |
| Substrate | Product | Substrate | Product |
|---|---|---|---|
 |  |  |  |
 |  |  |  |
 |  |  |  |
 |  |  |  |
 |  |  |  |
 |  |  |  |
 |  |  |  |
 |  |  |  |
 |  |
a Reaction conditions: alkenes (0.1 mmol, 1.0 equiv.), PhICl2 (0.11 mmol, 1.1 equiv.), 4-bromopyridine hydrochloride (0.3 mmol, 3.0 equiv.), TBABF4 (0.3 mmol, 3.0 equiv.) in DCM (4 mL) were stirred at r.t. for 1.5 h under N2, yields of isolated products. b Reaction conditions: alkenes (0.1 mmol, 1.0 equiv.), 9-(2-chlorophenyl) acridine (0.01 mmol, 10 mol%), 4-bromopyridine hydrochloride (0.1 mmol, 1.0 equiv.), TBABF4 (0.1 mmol, 1.0 equiv.) in DCM (4 mL) were irradiated with 380 nm blue LEDs at r.t. for 6 h under N2. |
本研究在前期的条件优化过程中发现, 溶剂的极性效应可显著调控多烯化合物的选择性官能团化(Scheme 2). 实验结果表明: 当以甲醇为溶剂时, 反应体系选择性地生成氯化/甲氧基化产物(3a~3d); 当以N,N-二甲基甲酰胺(DMF)为溶剂时可获得氯化/甲酰氧基化产物(3e); 而当添加水时则形成氯化/羟基化产物(3f). 值得注意的是, 该反应体系中会有氯负离子的形成, 且可作为亲核试剂, 致使二氯加成副产物生成, 这可能是目标产物收率偏低的关键限制因素. 尽管如此, 反应依然表现出优异的区域选择性, 其位点控制机制为多烯化合物的精准官能团化研究提供了创新性策略, 特别是为解决传统方法中区域选择性调控难题开辟了新的技术路径.
图式2 官能化考察Scheme 2 Investigation of functionalities a Reaction conditions: 1b (0.1 mmol, 1.0 equiv.), PhICl2 (0.11 mmol, 1.1 equiv.) in MeOH (4 mL) were stirred at r.t. for 1.5 h under N2. b Reaction conditions: 1b (0.1 mmol, 1.0 equiv.), PhICl2 (0.11 mmol, 1.1 equiv.) in DMF (4 mL) were stirred at r.t. for 1.5 h under N2. c Reaction conditions: 1b (0.1 mmol, 1.0 equiv.), PhICl2 (0.11 mmol, 1.1 equiv.) in MeCN/H2O (V∶V=1∶1, 4 mL) were stirred at r.t. for 1.5 h under N2. |
为深入探究本合成策略的潜在应用价值, 对产物2a开展了系统性转化研究(Scheme 3). 产物2a在碱性条件下可定向水解生成β,γ-不饱和醇4a, 成功实现形式上的香叶醇骨架远端烯烃位点修饰的同时, 完整保留了烯丙醇结构. 进一步研究发现, 烯丙基氯中C—Cl键表现出显著活化特性: 在DMF/80 ℃条件下与苯甲酸钾发生亲核取代, 经重排生成不饱和酯4b; 而与苯硫酚钠作用时, 通过协同双亲核机制, 同步实现C—Cl与C—酯基硫代, 获得双硫醚产物4c. 值得注意的是, 以PhICl2为氯化试剂继续进行多氯代时, 最终获得五氯代产物4d.
最后, 对反应机理进行了系统研究(Scheme 4): 自由基捕获实验表明, 加入2,2,6,6-四甲基哌啶氧化物(TEMPO)后原料转化受阻, 且产物收率降至22% (Scheme 4a), 该结果说明反应可能有自由基参与. 通过合成远端烯烃二氯加成产物(5), 验证其在碱性条件下无法生成消除产物(6), 排除了三级卤代烃经E2消除路径的可能性(Scheme 4b). 合成了三甲基硅醚的底物(7)进行反应探究, 在最佳反应条件下硅醚键发生断裂, 以57%的产率得到脱硅氯代产物(4a), 由此说明位阻效应对反应的选择性也产生了影响(Scheme 4c). 结合实验证据推测, 反应可能经历如下路径(Scheme 5): 二氯碘苯均裂产生氯自由基, 优先与富电子远端烯烃加成形成三级碳烷基自由基(I), 该中间体经氧化生成碳正离子(II), 在碱性条件下发生消除得到烯烃产物. 二氯碘苯可能兼具氯阳离子源功能, 协同促进碳正离子形成, 这种自由 基-离子协同机制为烯烃选择性官能化提供了新思路. 值得指出的是, 选择性源于酯基的强吸电子效应, 导致远端烯烃电子云密度相对较高, 同时不排除酯基的位阻效应对近端烯烃的空间屏蔽作用.
2 结论
本研究成功开发了一种以二氯碘苯为氯源的多烯选择性官能团化新策略, 实现了无需过渡金属催化、条件温和且高效的区域选择性转化. 该反应可通过调控添加物实现多烯化合物多样化的官能团化和位点精准调控, 并展现出优异的底物普适性与官能团兼容性, 为复杂多烯分子合成及药物修饰提供了绿色、实用的方法学工具.
3 实验部分
3.1 仪器与试剂
1H NMR (400 MHz)和13C NMR (100 MHz)采用德国Bruker 400 MHz核磁共振仪测定, CDCl3为溶剂; 高分辨率质谱(HRMS)采用电喷雾电离(ESI)技术在Bruker-micro-TOF-Q仪器上进行. 所有反应均在配备磁性搅拌元件的N2气氛下进行. 除非另有说明, 所有商用试剂均未进行额外纯化. 柱层析使用硅胶(200~300目), 以乙酸乙酯/石油醚体系作为流动相进行洗脱.
3.2 实验方法
将酯化的烯烃(0.1 mmol)、二氯碘苯(0.11 mmol)、4-溴-吡啶盐酸盐(0.3 mmol)、四丁基四氟硼酸铵(0.3 mmol)装入反应瓶中, 抽换氮气三次后加入二氯甲烷(DCM, 4 mL). 混合物在室温下搅拌, 反应完成后蒸去溶剂, 用硅胶柱层析纯化(洗脱液: 乙酸乙酯/石油醚), 得到产物1.
2-碘苯甲酸(E)-3,7-二甲基辛-2,6-二烯-1-酯(1a): 无色液体, 产率99% (1.92 g). 1H NMR (400 MHz, CDCl3) δ: 7.99~7.89 (m, 1H), 7.79~7.73 (m, 1H), 7.39~7.32 (m, 1H), 7.15~7.06 (m, 1H), 5.52~5.45 (m, 1H), 5.12~5.04 (m, 1H), 4.85 (d, J=7.2 Hz, 2H), 2.15~2.03 (m, 4H), 1.76 (s, 3H), 1.66 (s, 3H), 1.59 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.5, 142.9, 141.2, 135.5, 132.4, 131.8, 130.9, 127.8, 123.7, 118.0, 94.05, 62.5, 39.6, 26.3, 25.7, 17.8, 16.7; FT-IR ν: 2966, 2915, 1725, 1245, 1015, 739 cm－1; HRMS (ESI) calcd for C17H21INaO2 [M＋Na]＋407.0478, found 407.0471.
3-碘苯甲酸(E)-3,7-二甲基辛-2,6-二烯-1-酯(1b): 无色液体, 产率99% (1.90 g). 1H NMR (400 MHz, CDCl3) δ: 8.39~8.35 (m, 1H), 8.02~7.97 (m, 1H), 7.89~7.84 (m, 1H), 7.20~7.14 (m, 1H), 5.48~5.41 (m, 1H), 5.12~5.05 (m, 1H), 4.83 (d, J=6.8 Hz, 2H), 2.16~2.05 (m, 4H), 1.76 (s, 3H), 1.68 (s, 3H), 1.61 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 165.2, 142.9, 141.7, 138.6, 132.5, 132.0, 130.1, 128.9, 123.8, 118.2, 93.9, 62.4, 39.7, 26.4, 25.8, 17.8, 16.7; FT-IR ν: 2966, 2916, 1718, 1249, 1079, 743 cm－1; HRMS (ESI) calcd for C17H21INaO2 [M＋Na]＋ 407.0478, found 407.0471.
4-碘苯甲酸(E)-3,7-二甲基辛-2,6-二烯-1-酯(1c): 无色液体, 产率96% (1.85 g). 1H NMR (400 MHz, CDCl3) δ: 7.80~7.72 (m, 4H), 5.48~5.42 (m, 1H), 5.12~5.05 (m, 1H), 4.83 (d, J=7.2 Hz, 2H), 2.16~2.04 (m, 4H), 1.76 (s, 3H), 1.67~1.66 (m, 3H), 1.60 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.3, 142.8, 137.8, 132.0, 131.2, 130.1, 123.8, 118.3, 100.7, 62.3, 39.7, 26.4, 25.8, 17.8, 16.7; FT-IR ν: 2966, 2915, 1717, 1263, 1097, 752 cm－1; HRMS (ESI) calcd for C17H21INaO2 [M＋Na]＋ 407.0478, found 407.0473.
苯甲酸(E)-3,7-二甲基辛-2,6-二烯-1-酯(1d): 无色液体, 产率98% (1.26 g). 1H NMR (400 MHz, CDCl3) δ: 8.10~8.02 (m, 2H), 7.58~7.50 (m, 1H), 7.47~7.38 (m, 2H), 5.48 (t, J=6.4 Hz, 1H), 5.10 (t, J=6.4, 1H), 4.85 (d, J=7.2 Hz, 2H), 2.17~2.05 (m, 4H), 1.77 (s, 3H), 1.68 (s, 3H), 1.61 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 166.8, 142.5, 132.9, 131.9, 130.7, 129.7, 128.4, 123.9, 118.5, 62.0, 39.7, 26.4, 25.8, 17.81, 16.68; FT-IR ν: 2967, 2917, 1717, 1267, 1069, 709 cm－1; HRMS (ESI) calcd for C17H22NaO2 [M＋Na]＋ 281.1512, found 281.1506.
2-(2-碘苯基)乙酸(E)-3,7-二甲基辛-2,6-二烯-1-酯(1e): 无色液体, 产率92% (1.84 g). 1H NMR (400 MHz, CDCl3) δ: 7.88~7.81 (m, 1H), 7.33~7.27 (m, 2H), 6.99~6.92 (m, 1H), 5.40~5.34 (m, 1H), 5.12~5.06 (m, 1H), 4.66 (d, J=7.2 Hz, 2H), 3.80 (s, 2H), 2.14~2.02 (m, 4H), 1.70 (s, 3H), 1.69 (s, 3H), 1.61 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 170.6, 142.6, 139.6, 138.0, 131.9, 130.7, 128.9, 128.5, 123.9, 118.2, 101.1, 62.1, 46.4, 39.6, 26.4, 25.8, 17.8, 16.7; FT-IR ν: 2966, 2921, 1733, 1414, 1213, 733 cm－1; HRMS (ESI) calcd for C18H23INaO2 [M＋Na]＋ 421.0635, found 421.0629.
乙酸(E)-3,7-二甲基辛-2,6-二烯-1-酯(1f): 无色液体, 产率99% (1.38 g). 1H NMR (400 MHz, CDCl3) δ: 5.38~5.30 (m, 1H), 5.12~5.04 (m, 1H), 4.58 (d, J=7.2 Hz, 2H), 2.14~2.08 (m, 2H), 2.08~2.02 (m, 5H), 1.70 (s, 3H), 1.68 (s, 3H), 1.60 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 171.2, 142.3, 131.9, 123.8, 118.4, 61.5, 39.6, 26.4, 25.8, 21.1, 17.8, 16.5; FT-IR ν: 2968, 2919, 1738, 1228, 1022, 756 cm－1; HRMS (ESI) calcd for C12H20NaO2 [M＋Na]＋ 219.1356, found 219.1363.
烟酸(E)-3,7-二甲基辛-2,6-二烯-1-酯(1g): 无色液体, 产率93% (1.20 g). 1H NMR (400 MHz, CDCl3) δ: 9.25~9.18 (m, 1H), 8.78~8.71 (m, 1H), 8.33~8.24 (m, 1H), 7.40~7.32 (m, 1H), 5.46~5.40 (m, 1H), 5.11~5.02 (m, 1H), 4.86 (d, J=7.2 Hz, 2H), 2.13~2.03 (m, 4H), 1.76 (s, 3H), 1.65 (s, 3H), 1.59 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 165.2, 153.3, 150.9, 143.0, 137.0, 131.8, 126.4, 123.7, 123.2, 117.9, 62.2, 39.5, 26.2, 25.6, 17.7, 16.5; FT-IR ν: 2968, 2918, 1720, 1275, 740, 702 cm－1; HRMS (ESI) calcd for C16H21NNaO2 [M＋Na]＋ 282.1465, found 282.1462.
N-[(E)-3,7-二甲基辛-2,6-二烯-1-基]苯甲酰胺(1h): 无色液体, 产率99% (0.67 g). 1H NMR (400 MHz, CDCl3) δ: 7.81~7.72 (m, 2H), 7.51~7.45 (m, 1H), 7.44~7.37 (m, 2H), 6.07 (s, 1H), 5.34~5.26 (m, 1H), 5.11~5.04 (m, 1H), 4.05 (t, J=6 Hz, 2H), 2.15~2.02 (m, 4H), 1.72 (s, 3H), 1.68 (s, 3H), 1.60 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 167.4, 140.4, 134.8, 131.9, 131.4, 128.6, 127.0, 123.9, 119.9, 39.6, 38.1, 26.5, 25.8, 17.8, 16.4; FT-IR ν: 3307, 2916, 1634, 1537, 1291, 693 cm－1; HRMS (ESI) calcd for C17H24NO [M＋H]＋ 258.1852, found 258.1849.
苯甲酸(E)-4,8-二甲基壬-3,7-二烯-2-酯(1i): 无色液体, 产率97% (0.97 g). 1H NMR (400 MHz, CDCl3) δ: 8.07~8.02 (m, 2H), 7.56~7.49 (m, 1H), 7.45~7.39 (m, 2H), 5.90~5.81 (m, 1H), 5.32~5.26 (m, 1H), 5.12~5.04 (m, 1H), 2.14~2.07 (m, 2H), 2.06~1.99 (m, 2H), 1.79~1.75 (m, 3H), 1.67~1.64 (m, 3H), 1.60 (s, 3H), 1.40 (d, J=6.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.1, 139.7, 132.7, 131.8, 131.1, 129.7, 128.3, 124.9, 123.9, 68.9, 39.5, 26.4, 25.8, 21.1, 17.8, 16.8; FT-IR ν: 2973, 2928, 1714, 1268, 1037, 709 cm－1; HRMS (ESI) calcd for C18H24NaO2 [M＋Na]＋ 295.1669, found 295.1667.
苯甲酸6-甲基-2-亚甲基庚-5-烯-1-酯(1j): 无色液体, 产率80% (0.50 g). 1H NMR (400 MHz, CDCl3) δ: 8.11~8.05 (m, 2H), 7.59~7.53 (m, 1H), 7.48~7.41 (m, 2H), 5.19~5.11 (m, 2H), 5.02 (s, 1H), 4.79 (s, 2H), 2.25~2.15 (m, 4H), 1.69 (s, 3H), 1.62 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.4, 144.0, 133.1, 132.3, 130.4, 129.8, 128.5, 123.7, 112.6, 67.5, 33.5, 26.4, 25.8, 17.8; FT-IR ν: 2967, 2928, 1720, 1266, 1069, 708 cm－1; HRMS (ESI) calcd for C16H20NaO2 [M＋Na]＋ 267.1356, found 267.1350.
苯甲酸2,8-二甲基壬-2,7-二烯-4-酯(1k): 无色液体, 产率40% (0.38 g). 1H NMR (400 MHz, CDCl3) δ: 8.07~8.00 (m, 2H), 7.56~7.50 (m, 1H), 7.46~7.39 (m, 2H), 5.75~5.67 (m, 1H), 5.24~5.18 (m, 1H), 5.17~5.09 (m, 1H), 2.10~2.01 (m, 2H), 1.90~1.81 (m, 1H), 1.81~1.77 (m, 3H), 1.76~1.72 (m, 3H), 1.68~1.66 (m, 3H), 1.66~1.62 (m, 1H), 1.57 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.1, 137.4, 132.7, 132.3, 131.1, 129.7, 128.4, 123.9, 123.7, 72.2, 35.2, 25.9, 25.8, 24.0, 18.6, 17.9; FT-IR ν: 2968, 2915, 1714, 1267, 1109, 709 cm－1; HRMS (ESI) calcd for C18H24NaO2 [M＋Na]＋ 295.1669, found 295.1673.
苯甲酸(E)-9-甲基癸-3,8-二烯-5-酯(1l): 无色液体, 产率84% (0.66 g). 1H NMR (400 MHz, CDCl3) δ: 8.08~8.03 (m, 2H), 7.57~7.51 (m, 1H), 7.47~7.40 (m, 2H), 5.89~5.79 (m, 1H), 5.54~5.42 (m, 2H), 5.17~5.09 (m, 1H), 2.12~2.04 (m, 4H), 1.89~1.80 (m, 1H), 1.76~1.68 (m, 1H), 1.67 (s, 3H), 1.57 (s, 3H), 0.99 (t, J=7.6 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.0, 136.1, 132.8, 132.3, 131.0, 129.7, 128.4, 127.4, 123.6, 75.3, 34.9, 25.8, 25.4, 24.0, 17.8, 13.4; FT-IR ν: 2965, 2928, 1716, 1266, 756, 709 cm－1; HRMS (ESI) calcd for C18H24NaO2 [M＋Na]＋295.1669, found 295.1665.
苯甲酸7-甲基辛-1,6-二烯-3-酯(1m): 无色液体, 产率50% (0.25 g). 1H NMR (400 MHz, CDCl3) δ: 8.09~8.05 (m, 2H), 7.58~7.53 (m, 1H), 7.47~7.41 (m, 2H), 5.96~5.85 (m, 1H), 5.53~5.45 (m, 1H), 5.36~5.29 (m, 1H), 5.23~5.18 (m, 1H), 5.17~5.10 (m, 1H), 2.11 (q, J=7.6 Hz, 2H), 1.90~1.80 (m, 1H), 1.80~1.72 (m, 1H), 1.69~1.66 (m, 3H), 1.57 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.0, 136.7, 133.0, 132.5, 130.7, 129.7, 128.5, 123.4, 116.7, 75.1, 34.5, 25.8, 23.9, 17.8; FT-IR ν: 2967, 2917, 1718, 1267, 1109, 709 cm－1; HRMS (ESI) calcd for C16H20NaO2 [M＋Na]＋ 267.1356, found 267.1349.
苯甲酸(E)-7-甲基-1-苯基辛-1,6-二烯-3-酯(1n): 无色液体, 产率91% (0.79 g). 1H NMR (400 MHz, CDCl3) δ: 8.10~8.05 (m, 2H), 7.58~7.51 (m, 1H), 7.47~7.41 (m, 2H), 7.40~7.35 (m, 2H), 7.33~7.27 (m, 2H), 7.25~7.21 (m, 1H), 6.69 (d, J=16 Hz, 1H), 6.24 (q, J=7.2 Hz, 1H), 5.66 (q, J=6.4 Hz, 1H), 5.19~5.12 (m, 1H), 2.15 (q, J=7.2 Hz, 2H), 2.01~1.91 (m, 1H), 1.88~1.80 (m, 1H), 1.68 (s, 3H), 1.57 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.0, 136.6, 133.0, 132.7, 132.6, 130.9, 129.73, 128.7, 128.5, 128.0, 127.8, 126.7, 123.4, 75.1, 34.9, 25.8, 24.0, 17.8; FT-IR ν: 3061, 2915, 1715, 1266, 1069, 710 cm－1; HRMS (ESI) calcd for C22H24NaO2 [M＋Na]＋ 343.1669, found 343.1661.
苯甲酸(E)-2,7-二甲基-1-苯基辛-1,6-二烯-3-酯(1o): 无色液体, 产率51% (0.25 g). 1H NMR (400 MHz, CDCl3) δ: 8.12~8.07 (m, 2H), 7.59~7.53 (m, 1H), 7.49~7.42 (m, 2H), 7.36~7.30 (m, 2H), 7.30~7.27 (m, 2H), 7.25~7.19 (m, 1H), 6.62 (s, 1H), 5.55 (t, J=6.8 Hz, 1H), 5.21~5.15 (m, 1H), 2.17~2.09 (m, 2H), 2.02~1.93 (m, 4H), 1.91~1.82 (m, 1H), 1.72~1.68 (m, 3H), 1.59 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 165.9, 137.4, 136.1, 132.0, 132.6, 130.9, 129.7, 129.2, 128.5, 128.2, 127.9, 126.7, 123.5, 79.8, 33.3, 25.9, 24.3, 17.9, 13.9; FT-IR ν: 3059, 2917, 1716, 1450, 1266, 710 cm－1; HRMS (ESI) calcd for C23H26NaO2 [M＋Na]＋ 357.1825, found 357.1816.
苯甲酸5,9-二甲基-2-苯基癸-1,8-二烯-3-酯(1p): 无色液体, 产率50% (0.64 g). 1H NMR (400 MHz, CDCl3) δ: 8.14~8.01 (m, 2H), 7.61~7.56 (m, 1H), 7.53~7.44 (m, 4H), 7.40~7.28 (m, 3H), 6.07~5.98 (m, 1H), 5.39~5.35 (m, 1H), 5.32~5.29 (m, 1H), 5.06~4.97 (m, 1H), 1.95~1.86 (m, 2H), 1.74~1.63 (m, 5H), 1.61~1.59 (m, 3H), 1.56 (s, 1.5H), 1.53 (s, 1.5H), 0.93~0.89 (m, 3H), 13C NMR (101 MHz, CDCl3) δ: 166.1, 149.3, 139.7, 133.1, 131.4, 131.4, 130.7, 130.6, 129.8, 128.6, 128.5, 127.9, 127.3, 127.1, 124.7, 124.7, 114.2, 113.3, 75.1, 74.4, 41.79, 41.6, 37.5, 36.4, 29.4, 29.3, 25.8, 25.7, 25.5, 25.2, 20.1, 19.4, 17.8, 17.7; FT-IR ν: 2963, 2914, 1719, 1269, 1110, 709 cm－1; HRMS (ESI) calcd for C25H30NaO2 [M＋Na]＋ 385.2138, found 385.2137.
苯甲酸(1R,4R)-2-[1-苯甲酰氧基-5-甲基己-4-烯-1-基]双环[2.2.1]庚-5-烯-2-酯(1q): 无色液体, 产率49% (0.46 g). 1H NMR (400 MHz, CDCl3) δ: 8.12~7.99 (m, 2H), 7.60~7.51 (m, 1H), 7.49~7.40 (m, 2H), 6.22~6.16 (m, 0.5H), 6.16~6.12 (m, 0.3H), 6.10~6.05 (m, 0.7 H), 5.97~5.93 (m, 0.5H), 5.24~5.16 (m, 0.3H), 5.14~5.04 (m, 1.2H), 4.76~4.69 (m, 0.25H), 4.66~4.59 (m, 0.25H), 2.90~2.77 (m, 1.5H), 2.72~2.63 (m, 0.5H), 2.47~2.37 (m, 0.5H), 2.10~1.98 (m, 2H), 1.89~1.67 (m, 3H), 1.64~1.61 (m, 3H), 1.59 (s, 0.5H), 1.54 (d, J=6.8 Hz, 3H), 1.47~1.40 (m, 1H), 1.34~1.28 (m, 1H), 1.24~1.18 (m, 0.24H), 0.91~0.83 (m, 0.5H), 0.70~0.64 (m, 0.26H); 13C NMR (101 MHz, CDCl3) δ: 166.6, 166.5, 166.4, 138.3, 137.5, 137.3, 137.1, 136.9, 136.8, 133.2, 132.9, 132.8, 132.1, 132.0, 131.7, 131.0, 130.9, 130.8, 129.8, 129.7, 129.7, 128.5, 128.4, 124.1, 123.9, 79.3, 78.3, 49.9, 49.1, 46.0, 45.6, 44.8, 44.4, 43.9, 43.7, 43.6, 42.4, 42.2, 41.9, 34.5, 34.1, 34.1, 30.4, 29.8, 29.1, 25.8, 24.1, 24.1, 23.7, 17.8; FT-IR ν: 3060, 2967, 1714, 1269, 1026, 708 cm－1; HRMS (ESI) calcd for C21H26NaO2 [M＋Na]＋ 333.1825, found 333.1821.
2-碘苯甲酸(E)-6-氯-3,7-二甲基辛-2,7-二烯-1-酯(2a): 无色液体, 产率96% (40 mg). 1H NMR (400 MHz, CDCl3) δ: 7.99~7.95 (m, 1H), 7.79~7.75 (m, 1H), 7.42~7.36 (m, 1H), 7.16~7.11 (m, 1H), 5.56~5.48 (m, 1H), 5.01 (s, 1H), 4.92~4.88 (m, 1H), 4.85 (d, J=7.2 Hz, 2H), 4.36 (t, J=7.2 Hz, 1H), 2.23~2.08 (m, 2H), 2.04~1.91 (m, 2H), 1.81 (s, 3H), 1.78 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.7, 144.3, 141.4, 141.3, 135.6, 132.6, 131.0, 128.0, 119.2, 114.51, 94.1, 66.2, 62.4, 36.6, 34.5, 17.2, 16.8; FT-IR ν: 2948, 1724, 1285, 1245, 1042, 740 cm－1; HRMS (ESI) calcd for C17H20ClINaO2 [M＋Na]＋ 441.0089, found 441.0094.
3-碘苯甲酸(E)-6-氯-3,7-二甲基辛-2,7-二烯-1-酯(2b): 无色液体, 产率96% (40 mg). 1H NMR (400 MHz, CDCl3) δ: 8.37 (s, 1H), 8.00 (d, J=7.6 Hz, 1H), 7.86 (d, J=7.6 Hz, 1H), 7.18 (t, J=7.6 Hz, 1H), 5.49 (t, J=6.8 Hz, 1H), 5.01 (s, 1H), 4.94~4.88 (m, 1H), 4.84 (d, J=7.2 Hz, 2H), 4.35 (t, J=6.8 Hz, 1H), 2.25~2.09 (m, 2H), 2.04~1.89 (m, 2H), 1.82 (s, 3H), 1.78 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 165.2, 144.3, 141.8, 141.2, 138.6, 132.4, 130.2, 128.9, 119.3, 114.5, 93.9, 66.2, 62.2, 36.7, 34.5, 17.2, 16.7; FT-IR ν: 3064, 2922, 1717, 1249, 1080, 705 cm－1; HRMS (ESI) calcd for C17H20ClINaO2 [M＋ Na]＋ 4441.0089, found 441.0092.
4-碘苯甲酸(E)-6-氯-3,7-二甲基辛-2,7-二烯-1-酯(2c): 无色液体, 产率96% (40 mg). 1H NMR (400 MHz, CDCl3) δ: 7.81~7.77 (m, 2H), 7.75~7.72 (m, 2H), 5.51~5.45 (m, 1H), 5.00 (s, 1H), 4.91~4.88 (m, 1H), 4.82 (d, J=7.2 Hz, 2H), 4.35 (t, J=7.2 Hz, 1H), 2.20~2.07 (m, 2H), 2.02~1.91 (m, 2H), 1.81 (s, 3H), 1.77 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.2, 144.3, 141.1, 137.8, 131.2, 130.0, 119.4, 114.5, 100.8, 66.2, 62.1, 36.7, 34.5, 17.2, 16.7; FT-IR ν: 2921, 2852, 1717, 1264, 1097, 733 cm－1; HRMS (ESI) calcd for C17H20ClINaO2 [M＋ Na]＋ 441.0089, found 441.0092.
苯甲酸(E)-6-氯-3,7-二甲基辛-2,7-二烯-1-酯(2d): 无色液体, 产率91% (27 mg). 1H NMR (400 MHz, CDCl3) δ: 8.06~8.03 (m, 2H), 7.58~7.53 (m, 1H), 7.46~7.41 (m, 2H), 5.54~5.47 (m, 1H), 5.01 (s, 1H), 4.92~4.89 (m, 1H), 4.84 (d, J=7.2 Hz, 2H), 4.36 (t, J=7.2 Hz, 1H), 2.24~2.09 (m, 2H), 2.07~1.92 (m, 2H), 1.81 (s, 3H), 1.78 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.7, 144.3, 140.8, 133.0, 130.5, 129.7, 128.5, 119.6, 114.5, 66.3, 61.8, 36.7, 34.5, 17.1, 16.7; FT-IR ν: 2949, 1716, 1267, 1069, 806, 709 cm－1; HRMS (ESI) calcd for C17H21ClNaO2 [M＋Na]＋ 315.1122, found 315.1118.
2-(2-碘苯基)乙酸(E)-6-氯-3,7-二甲基辛-2,7-二烯-1-酯(2e): 无色液体, 产率79% (34 mg). 1H NMR (400 MHz, CDCl3) δ: 7.87~7.81 (m, 1H), 7.58~7.53 (m, 2H), 6.99~6.93 (m, 1H), 5.39 (t, J=7.2 Hz, 1H), 4.99 (s, 1H), 4.90 (s, 1H), 4.65 (d, J=7.2 Hz, 2H), 4.33 (t, J=7.6 Hz, 1H), 3.80 (s, 2H), 2.19~2.04 (m, 2H), 2.02~1.88 (m, 2H), 1.70 (s, 3H), 1.78 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 170.6, 144.2, 141.0, 139.6, 137.9, 130.8, 129.0, 128.6, 119.4, 114.5, 101.1, 66.2, 61.9, 46.4, 36.6, 34.5, 17.2, 16.6; FT-IR ν: 3056, 2921, 1733, 1317, 1154, 732 cm－1; HRMS (ESI) calcd for C18H22ClINaO2 [M＋Na]＋ 455.0245, found 455.0239.
乙酸(E)-6-氯-3,7-二甲基辛-2,7-二烯-1-酯(2f): 无色液体, 产率73% (17 mg). 1H NMR (400 MHz, CDCl3) δ: 5.40~5.34 (m, 1H), 5.02~5.49 (m, 1H), 4.91~4.88 (m, 1H), 4.58 (d, J=6.8 Hz, 2H), 4.34 (t, J=7.6 Hz, 1H), 2.18~2.12 (m, 1H), 2.06~2.03 (m, 4H), 2.00~1.88 (m, 2H), 1.82~1.80 (m, 3H), 1.71 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 171.2, 144.32, 140.7, 119.5, 114.5, 66.2, 61.3, 36.6, 34.5, 21.2, 17.1, 16.6; FT-IR ν: 2919, 2851, 1737, 1366, 1229, 1022 cm－1; HRMS (ESI) calcd for C12H19ClNaO2 [M＋Na]＋ 253.0966, found 253.0961.
烟酸(E)-6-氯-3,7-二甲基辛-2,7-二烯-1-酯(2g): 无色液体, 产率60% (18 mg). 1H NMR (400 MHz, CDCl3) δ: 9.23 (s, 1H), 8.82~8.74 (m, 1H), 8.33~8.28 (m, 1H), 7.43~7.37 (m, 1H), 5.54~5.47 (m, 1H), 5.00 (s, 1H), 4.92~4.89 (m, 1H), 4.88 (d, J=7.2 Hz, 2H), 4.35 (t, J=7.2 Hz, 1H), 2.23~2.08 (m, 2H), 2.02~1.91 (m, 2H), 1.83~1.80 (m, 3H), 1.79 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 165.4, 153.5, 151.1, 144.2, 141.5, 137.2, 126.4, 123.4, 119.1, 114.5, 66.2, 62.2, 36.7, 34.5, 17.2, 16.7; FT-IR ν: 2923, 2854, 1720, 1275, 1110, 740 cm－1; HRMS (ESI) calcd for C16H21ClNO2 [M＋H]＋ 294.1255, found 294.1251.
N-[(E)-6-氯-3,7-二甲基辛-2,7-二烯-1-基]苯甲酰胺(2h): 无色液体, 产率89% (26 mg). 1H NMR (400 MHz, CDCl3) δ: 7.78~7.74 (m, 2H), 7.50~7.46 (m, 1H), 7.45~7.40 (m, 2H), 6.08 (s, 1H), 5.36~5.30 (m, 1H), 5.0 (s, 1H), 4.91~4.88 (m, 1H), 4.34 (t, J=7.2 Hz, 1H), 4.06 (t, J=6.4 Hz, 2H), 2.20~2.04 (m, 2H), 2.02~1.90 (m, 2H), 1.81 (s, 3H), 1.73 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 167.5, 144.4, 138.7, 134.7, 131.5, 128.7, 127.0, 121.1, 114.4, 66.4, 38.1, 36.7, 34.7, 17.2, 16.5; FT-IR ν: 3307, 2920, 1635, 1536, 1290, 693 cm－1; HRMS (ESI) calcd for C17H22ClNNaO [M＋Na]＋ 314.1282, found 314.1280.
苯甲酸(E)-7-氯-4,8-二甲基壬-3,8-二烯-2-酯(2i): 无色液体, 产率62% (19 mg). 1H NMR (400 MHz, CDCl3) δ: 8.06~8.00 (m, 2H), 7.56~7.51 (m, 1H), 7.45~7.40 (m, 2H), 5.87~5.79 (m, 1H), 5.35~5.30 (m, 1H), 4.99 (s, 1H), 4.91~4.87 (m, 1H), 4.34 (t, J=7.6, 1H), 2.20~2.05 (m, 2H), 2.02~1.90 (m, 2H), 1.80 (s, 3H), 1.79~1.77 (m, 3H), 1.43~1.38 (m, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.1, 144.4, 138.2, 138.1, 132.8, 131.0, 129.7, 128.4, 125.9, 125.9, 114.4, 68.8, 66.2, 36.6, 34.5, 34.5, 21.1, 21.1, 17.1, 16.8, 16.8; FT-IR ν: 2977, 2930, 1713, 1314, 1175, 710 cm－1; HRMS (ESI) calcd for C18H23ClNaO2 [M＋ Na]＋ 329.1279, found 329.1275.
苯甲酸5-氯-6-甲基-2-亚甲基庚-6-烯-1-酯(2j): 无色液体, 产率73% (20 mg). 1H NMR (400 MHz, CDCl3) δ: 8.09~8.04 (m, 2H), 7.60~7.54 (m, 1H), 7.48~7.43 (m, 2H), 5.20(s, 1H), 5.04 (d, J=9.6 Hz, 2H), 4.93~4.89 (m, 1H), 4.78 (s, 2H), 4.44~4.39 (m, 1H), 2.32~2.18 (m, 2H), 2.10~2.00 (m, 2H), 1.81 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.4, 144.3, 142.6, 133.2, 129.8, 128.5, 114.6, 113.7, 67.3, 66.1, 34.5, 30.6, 17.21; FT-IR ν: 2933, 1720, 1451, 1266, 1109, 708 cm－1; HRMS (ESI) calcd for C16H19ClNaO2 [M＋Na]＋ 301.0966, found 301.0964.
苯甲酸7-氯-2,8-二甲基壬-2,8-二烯-4-酯(2k): 无色液体, 产率53% (16 mg). 1H NMR (400 MHz, CDCl3) δ: 8.05~8.01 (m, 2H), 7.57~7.52 (m, 1H), 7.46~7.40 (m, 2H), 5.78~5.69 (m, 1H), 5.25~5.19 (m, 1H), 5.04~5.00 (m, 1H), 4.92~4.89 (m, 1H), 4.45~4.37 (m, 1H), 2.02~1.82 (m, 3H), 1.81~1.78 (m, 6H), 1.78 (s, 3H), 1.71~1.64 (m, 1H); 13C NMR (101 MHz, CDCl3) δ: 166.2, 144.2, 138.0, 132.9, 130.8, 129.7, 128.5, 123.4, 123.3, 114.6, 71.7, 71.5, 66.6, 66.4, 32.6, 32.4, 32.2, 26.0, 18.7, 17.1, 17.0; FT-IR ν: 2921, 2855, 1714, 1450, 1268, 710 cm－1; HRMS (ESI) calcd for C18H23ClNaO2 [M＋Na]＋329.1279, found 329.1274.
苯甲酸(E)-8-氯-9-甲基癸-3,9-二烯-5-酯(2l): 无色液体, 产率56% (17 mg). 1H NMR (400 MHz, CDCl3) δ: 8.07~8.02 (m, 2H), 7.59~7.53 (m, 1H), 7.44 (t, J=7.6 Hz, 2H), 5.91~5.82 (m, 1H), 5.55~5.42 (m, 2H), 5.04~5.00 (m, 1H), 4.90 (s, 1H), 4.45~4.38 (m, 1H), 2.10~2.03 (m, 2H), 1.98~1.85 (m, 3H), 1.79 (d, J=4.4 Hz, 3H), 1.77~1.69 (m, 1H), 0.99 (t, J=7.6 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.0, 144.2, 144.2, 136.6, 133.0, 130.7, 129.7, 128.5, 126.9, 126.8, 114.6, 114.6, 75.0, 74.7, 66.5, 66.39, 32.49, 32.30, 32.26, 32.14, 25.4, 17.1, 17.1, 13.3; FT-IR ν: 2963, 2926, 1715, 1266, 1109, 710 cm－1; HRMS (ESI) calcd for C18H23ClNaO2 [M＋ Na]＋ 329.1279, found 329.1273.
苯甲酸6-氯-7-甲基辛-1,7-二烯-3-酯(2m): 无色液体, 产率63% (17 mg). 1H NMR (400 MHz, CDCl3) δ: 8.08~8.04 (m, 2H), 7.59~7.54 (m, 1H), 7.48~7.43 (m, 2H), 5.93~5.84 (m, 1H), 5.56~5.49 (m, 1H), 5.38~5.36 (m, 0.5H), 5.34~5.31 (m, 0.5H), 5.26~5.24 (m, 0.5H), 5.24~5.22 (m, 0.5H), 5.04~5.01 (m, 1H), 4.92~4.89 (m, 1H), 4.45~4.38 (m, 1H), 2.02~1.89 (m, 3H), 1.81~1.78 (m, 3H), 1.78~1.73 (m, 1H); 13C NMR (101 MHz, CDCl3) δ: 165.9, 144.1, 136.1, 133.2, 130.4, 129.7, 128.6, 117.4, 114.7, 114.6, 74.7, 74.4, 66.4, 66.3, 32.3, 32.1, 31.8, 31.7, 17.2, 17.1; FT-IR ν: 3084, 2921, 1717, 1266, 1110, 710 cm－1; HRMS (ESI) calcd for C16H19ClNaO2 [M＋ Na]＋ 301.0966, found 301.0961.
苯甲酸(E)-6-氯-7-甲基-1-苯基辛-1,7-二烯-3-酯(2n): 无色液体, 产率30% (11 mg). 1H NMR (400 MHz, CDCl3) δ: 8.10~8.05 (m, 2H), 7.58 (t, J=7.6 Hz, 1H), 7.46 (t, J=7.6 Hz, 2H), 7.41~7.37 (m, 2H), 7.32 (t, J=7.2 Hz, 2H), 7.28~7.26 (m, 1H), 6.75~6.67 (m, 1H), 6.23 (q, J=7.2 Hz, 1H), 5.74~5.65 (m, 1H), 5.04 (s, 1H), 4.93~4.89 (m, 1H), 4.47~4.40 (m, 1H), 2.08~1.89 (m, 4H), 1.81 (d, J=4.8 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 165.9, 144.1, 136.3, 133.2, 130.5, 129.8, 128.7, 128.6, 128.2, 127.1, 126.8, 114.74, 114.69, 74.8, 74.5, 66.4, 66.3, 32.5, 32.3, 32.2, 17.2, 17.1; FT-IR ν: 3029, 2922, 1715, 1266, 1109, 710 cm－1; HRMS (ESI) calcd for C22H23Cl- NaO2 [M＋Na]＋ 377.1279, found 377.1278.
苯甲酸(E)-6-氯-2,7-二甲基-1-苯基辛-1,7-二烯-3-酯(2o): 无色液体, 产率42% (16 mg). 1H NMR (400 MHz, CDCl3) δ: 8.10~8.06 (m, 2H), 7.60~7.55 (m, 1H), 7.49~7.43 (m, 2H), 7.34~7.30 (m, 2H), 7.30~7.26 (m, 2H), 7.25~7.20 (m, 1H), 6.62 (s, 1H), 5.61~5.53 (m, 1H), 5.05 (s, 1H), 4.94~4.90 (m, 1H), 4.50~4.41 (m, 1H), 2.07~2.00 (m, 1H), 1.99~1.92 (m, 5H), 1.92~1.86 (m, 1H), 1.81 (d, J=4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 165.8, 144.1, 137.1, 135.6, 133.2, 130.5, 129.8, 129.2, 128.8, 128.6, 128.3, 128.2, 126.9, 114.7, 79.4, 79.1, 66.5, 66.3, 32.8, 32.6, 30.6, 30.4, 17.2, 17.2, 14.0, 13.9. FT-IR ν: 3061, 2923, 1716, 1266, 1110, 710 cm－1; HRMS (ESI) calcd for C23H25ClNaO2 [M＋Na]＋ 391.1435, found 391.1434.
苯甲酸-2-苯基-5,9-二甲基-8-氯癸-1,9-二烯-3-酯(2p): 无色液体, 产率73% (29 mg). 1H NMR (400 MHz, CDCl3) δ: 8.14~8.09 (m, 2H), 7.62~7.56 (m, 1H), 7.53~7.47 (m, 4H), 7.39~7.31 (m, 3H), 6.05~5.96 (m, 1H), 5.40~5.35 (m, 1H), 5.34~5.29 (m, 1H), 4.95~4.89 (m, 1H), 4.86~4.81 (m, 1H), 4.30~4.22 (m, 1H), 1.91~1.80 (m, 1H), 1.79~1.68 (m, 6H), 1.67~1.61 (m, 1H), 1.53~1.42 (m, 1H), 1.40~1.28 (m, 1H), 0.94~0.89 (m, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.0, 149.3, 148.9, 144.5, 144.4, 144.4, 144.3, 139.5, 133.2, 133.2, 130.6, 130.5, 129.8, 128.6, 128.6, 128.0, 127.3, 127.1, 114.6, 114.5, 114.4, 114.4, 114.3, 114.2, 113.3, 75.1, 75.0, 74.3, 74.2, 67.1, 67.0, 41.8, 41.3, 41.3, 34.6, 34.5, 34.1, 34.1, 33.7, 33.6, 33.5, 29.5, 29.4, 20.1, 20.0, 19.4, 19.3, 17.0, 16.9; FT-IR ν: 2955, 2927, 1718, 1269, 1110, 709 cm－1; HRMS (ESI) calcd for C25H29ClNaO2 [M＋Na]＋ 419.1748, found 419.1747.
苯甲酸-1-[(1R,4R)-二环[2.2.1]庚-5-烯-2-基]-4-氯-5-甲基己-5-烯-1-酯(2q): 无色液体, 产率74% (26 mg). 1H NMR (400 MHz, CDCl3) δ: 8.11~7.98 (m, 2H), 7.60~7.53 (m, 1H), 7.46~7.41 (m, 2H), 7.49~7.41 (m, 1H), 6.24~6.13 (m, 0.8H), 6.11~6.06 (m, 0.6H), 6.01~5.97 (m, 0.2H), 5.96~5.90 (m, 0.4H), 5.23~5.15 (m, 0.25H), 5.12~5.04 (m, 0.25H), 5.03~4.95 (m, 1H), 4.78~4.70 (m, 0.25H), 4.65~4.58 (m, 0.25H), 4.46~4.33 (m, 1H), 2.89~2.78 (m, 1.5H), 2.74~2.62 (m, 0.5H), 2.46~2.40 (m, 0.5H), 1.97~1.80 (m, 4H), 1.78~1.73 (m, 3H), 1.63~1.55 (m, 1.5H), 1.46~1.41 (m, 1H), 1.35~1.29 (m, 1H), 1.24~1.21 (m, 0.24H), 0.89~0.82 (m, 0.5H), 0.70~0.64 (m, 0.26H); 13C NMR (101 MHz, CDCl3) δ: 166.5, 144.4, 144.1, 138.5, 137.8, 137.4, 136.7, 133.09, 133.0, 131.6, 130.7, 129.8, 129.8, 129.7, 128.6, 128.5, 114.7, 114.4, 114.3, 66.7, 66.6, 49.9, 49.1, 46.0, 45.5, 44.7, 44.4, 43.7, 43.5, 42.4, 42.2, 41.9, 32.3, 32.1, 31.7, 31.5, 31.2, 30.9, 30.4, 29.8, 29.7, 29.5, 27.4, 17.3, 16.8, 14.2; FT-IR ν: 3062, 2963, 1712, 1269, 755, 709 cm－1; HRMS (ESI) calcd for C21H25ClNaO2 [M＋Na]＋367.1435, found 367.1436.
(E)-6-氯-7-甲氧基-3,7-二甲基辛-2-烯-1-基-2-碘苯甲酸酯(3a): 无色液体, 产率43% (19 mg). 1H NMR (400 MHz, CDCl3) δ: 7.97 (d, J=8 Hz, 1H), 7.80~7.74 (m, 1H), 7.41~7.35 (m, 1H), 7.16~7.10 (m, 1H), 5.56 (t, J=6.8 Hz, 1H), 4.86 (d, J=6.8 Hz, 1H), 4.92~4.89 (m, 1H), 3.80~3.74 (m, 1H), 3.20 (s, 3H), 2.44~2.36 (m, 1H), 2.22~2.08 (m, 2H), 1.78 (s, 3H), 1.67~1.61 (m, 1H), 1.27 (s, 3H), 1.22 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.7, 141.9, 141.3, 135.6, 132.6, 131.0, 128.0, 119.1, 94.1, 68.2, 62.5, 49.8, 37.1, 30.44, 22.9, 20.7, 16.7; FT-IR ν: 3080, 2949, 1728, 1431, 1245, 739 cm－1; HRMS (ESI) calcd for C18H24ClINaO3 [M＋Na]＋ 473.0351, found 473.0349.
(E)-6-氯-7-甲氧基-3,7-二甲基辛-2-烯-1-基苯甲酸酯(3b): 无色液体, 产率40% (13 mg). 1H NMR (400 MHz, CDCl3) δ: 8.07~8.02 (m, 2H), 7.58~7.52 (m, 1H), 7.46~7.40 (m, 2H), 5.54 (t, J=6.8 Hz, 1H), 4.85 (d, J=6.8 Hz, 2H), 3.81~3.75 (m, 1H), 3.20 (s, 3H), 2.45~2.37 (m, 1H), 2.22~2.06 (m, 2H), 1.78 (s, 3H), 1.69~1.63 (m, 1H), 1.28 (s, 3H), 1.23 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.7, 141.3, 133.0, 130.5, 129.7, 128.4, 119.6, 68.2, 61.9, 49.7, 37.1, 30.5, 22.8, 20.8, 16.7; FT-IR ν: 2980, 2936, 1716, 1268, 1097, 710 cm－1; HRMS (ESI) calcd for C18H26ClO3 [M＋H]＋ 325.1565, found 325.1566.
5-氯-6-甲氧基-6-甲基-2-亚甲基庚基苯甲酸酯(3c): 无色液体, 产率52% (16 mg). 1H NMR (400 MHz, CDCl3) δ: 8.10~8.06 (m, 2H), 7.60~7.54 (m, 1H), 7.48~7.42 (m, 2H), 5.19 (s, 1H), 5.07 (s, 1H), 4.80 (s, 2H), 3.85~3.80 (m, 1H), 3.22 (s, 3H), 2.58~2.48 (m, 1H), 2.30~2.17 (m, 2H), 1.77~1.70 (m, 1H), 1.29 (s, 3H), 1.23 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.4, 143.0, 133.2, 130.3, 129.8, 128.5, 113.5, 68.4, 67.3, 49.8, 31.1, 30.6, 22.9, 20.6; FT-IR ν: 2979, 2935, 1720, 1267, 1070, 709 cm－1; HRMS (ESI) calcd for C17H23ClNaO3 [M＋Na]＋ 333.1228, found 333.1228.
8-氯-9-甲氧基-5,9-二甲基-2-苯基癸-1-烯-3-基苯甲酸酯(3d): 无色液体, 产率36% (16 mg). 1H NMR (400 MHz, CDCl3) δ: 8.15~8.10 (m, 2H), 7.62~7.56 (m, 1H), 7.54~7.45 (m, 4H), 7.39~7.28 (m, 3H), 6.08~5.98 (m, 1H), 5.41~5.29 (m, 2H), 3.74~3.64 (m, 1H), 3.20 (d, J=5.2 Hz, 1.5H), 3.18 (s, 1.5H), 1.95~1.65 (m, 4H), 1.59~1.34 (m, 3H), 1.25 (d, J=2.8 Hz, 1.5H), 1.23 (d, J=4.4 Hz, 1.5H), 1.19 (s, 1.5H), 1.15 (d, J=5.2 Hz, 1.5H), 0.96~0.89 (m, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.0, 149.4, 149.0, 148.9, 139.6, 133.1, 133.1, 130.6, 129.8, 128.6, 128.0, 128.0, 127.3, 127.3, 127.1, 114.7, 114.3, 113.2, 75.4, 75.0, 74.3, 74.3, 69.6, 69.6, 69.5, 69.3, 49.7, 49.7, 49.7, 42.2, 41.7, 41.5, 40.9, 35.4, 35.3, 34.6, 34.0, 30.1, 30.0, 29.7, 29.6, 29.5, 29.4, 29.4, 22.8, 22.7, 20.8, 20.4, 20.0, 19.7, 19.1; FT-IR ν: 2987, 2987, 1718, 1269, 1070, 709 cm－1; HRMS (ESI) calcd for C26H33Cl- NaO3 [M＋Na]＋ 451.2010, found 451.2003.
(E)-6-氯-7-(甲酰氧基)-3,7-二甲基辛-2-烯-1-基-2-碘苯甲酸酯(3e): 无色液体, 产率50% (23 mg). 1H NMR (400 MHz, CDCl3) δ: 8.01~7.96 (m, 2H), 7.82~7.76 (m, 1H), 7.42~7.36 (m, 1H), 7.17~7.11 (m, 1H), 5.59~5.52 (m, 1H), 4.86 (d, J=7.2 Hz, 2H), 4.27~4.21 (m, 1H), 2.46~2.38 (m, 1H), 2.23~2.14 (m, 1H), 2.06~1.97 (m, 1H), 1.78 (s, 3H), 1.75~1.69 (m, 1H), 1.60 (s, 3H), 1.59 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.7, 160.0, 141.4, 141.3, 135.5, 132.7, 131.0, 128.0, 119.4, 94.1, 84.8, 66.9, 62.4, 36.9, 30.5, 23.9, 22.6, 16.8; FT-IR ν: 2987, 2927, 1718, 1246, 1125, 741 cm－1; HRMS (ESI) calcd for C18H22ClINaO4 [M＋Na]＋ 487.0144, found 487.0140.
(E)-1-[(2-碘苯甲酰)氧基]-6-氯-3,7-二甲基辛-2-烯- 7-醇(3f): 无色液体, 产率23% (12 mg). 1H NMR (400 MHz, CDCl3) δ: 8.00~7.95 (m, 1H), 7.81~7.74 (m, 1H), 7.43~7.37 (m, 1H), 7.18~7.11 (m, 1H), 5.59~5.52 (m, 1H), 4.86 (d, J=7.2 Hz, 2H), 3.84~3.77 (m, 1H), 2.46~2.37 (m, 1H), 2.24~2.15 (m, 1H), 2.05~1.98 (m, 1H), 1.79 (s, 3H), 1.75~1.70 (m, 1H), 1.30 (s, 3H), 1.29 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.8, 141.5, 141.4, 135.6, 132.6, 131.0, 128.0, 119.4, 94.1, 73.4, 72.9, 62.4, 37.1, 31.0, 26.5, 25.5, 16.7; FT-IR ν: 2955, 2928, 2858, 2159, 1718, 825 cm－1; HRMS (ESI) calcd for C17H22ClI- NaO3 [M＋Na]＋ 459.0194, found 459.0190.
(E)-6-氯-3,7-二甲基辛-2,7-二烯-1-醇(4a): 无色液体, 产率85% (26 mg). 1H NMR (400 MHz, CDCl3) δ: 5.43 (t, J=7.2 Hz, 1H), 5.00 (s, 1H), 4.90 (s, 1H), 4.34 (t, J=7.6 Hz, 1H), 4.15 (d, J=6.8 Hz, 2H), 2.17~1.91 (m, 4H), 1.80 (s, 3H), 1.67 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 144.3, 138.1, 124.5, 114.4, 66.3, 59.4, 36.6, 34.6, 17.1, 16.4; FT-IR ν: 3339, 2923, 1443, 1375, 998, 906 cm－1; HRMS (ESI) calcd for C10H17ClNaO [M＋Na]＋ 211.0860, found 211.0858.
(2E,6E)-8-(苯甲酰氧基)-3,7-二甲基辛-2,6-二烯-1-基-2-碘苯甲酸酯(4b): 无色液体, 产率96% (87 mg). 1H NMR (400 MHz, CDCl3) δ: 8.07~8.02 (m, 2H), 7.99~7.95 (m, 1H), 7.80~7.75 (m, 1H), 7.58~7.52 (m, 1H), 7.46~7.40 (m, 2H), 7.40~7.35 (m, 1H), 7.15~7.10 (m, 1H), 5.56~5.40 (m, 2H), 4.88~4.82 (m, 3.55H), 4.70 (s, 0.45H), 2.35~2.21 (m, 2H), 2.17~2.10 (m, 2H), 1.84~1.81 (m, 2.3H), 1.80~1.67 (m, 3H), 1.74 (s, 0.7H); 13C NMR (101 MHz, CDCl3) δ: 166.7, 142.3, 141.3, 135.6, 133.0, 133.0, 132.6, 131.0, 131.0, 130.5, 130.4, 130.0, 129.7, 128.8, 128.5, 128.0, 118.6, 94.1, 70.6, 63.7, 62.5, 39.6, 39.0, 26.1, 21.7, 16.7, 14.2; FT-IR ν: 3062, 2922, 1715, 1267, 1246, 710 cm－1; HRMS (ESI) calcd for C24H25INaO4 [M＋Na]＋ 527.0690, found 527.0686.
(E)-1,6-二(苯硫基)-3,7-二甲基辛-2,7-二烯(4c): 无色液体, 产率61% (61 mg). 1H NMR (400 MHz, CDCl3) δ: 7.37~7.31 (m, 5H), 7.29~7.27 (m, 1H), 7.26~7.23 (m, 2H), 7.22~7.15 (m, 2H), 5.36~5.30 (m, 1H), 4.74~4.71 (m, 1H), 4.58 (s, 1H), 3.57~3.53 (m, 3H), 2.08 (t, J=7.6 Hz, 2H), 1.76 (s, 3H), 1.75~1.67 (m, 2H), 1.56 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 143.5, 138.9, 136.7, 135.4, 132.7, 130.0, 128.9, 128.7, 127.1, 126.2, 120.4, 114.0, 55.7, 37.3, 32.3, 30.7, 17.9, 16.1; FT-IR ν: 3073, 2919, 1479, 1438, 736, 689 cm－1; HRMS (ESI) calcd for C22H26NaS2 [M＋Na]＋ 377.1368, found 377.1368.
2-碘苯甲酸-2,3,6,7,8-五氯-3,7-二甲基辛酯(4d): 黄色液体, 产率96% (135 mg). 1H NMR (400 MHz, CDCl3) δ: 8.06~7.99 (m, 1H), 7.93~7.87 (m, 1H), 7.46~7.40 (m, 1H), 7.22~7.15 (m, 1H), 5.09~5.00 (m, 1H), 4.65~4.57 (m, 1H), 4.42~4.34 (m, 1H), 4.24~4.13 (m, 1.43H), 4.02~3.97 (m, 0.5H), 3.86~3.80 (m, 0.5H), 3.74~3.69 (m, 0.47H), 2.58~1.96 (m, 4H), 1.79~1.74 (m, 2.5H), 1.73~1.68 (m, 3.5H); 13C NMR (101 MHz, CDCl3) δ: 165.9, 141.7, 134.2, 133.2, 131.5, 131.4, 128.1, 94.6, 72.6, 72.1, 72.0, 67.2, 67.1, 66.6, 66.6, 66.5, 65.9, 65.6, 65.5, 65.4, 65.0, 64.6, 64.2, 63.8, 53.0, 52.9, 52.8, 51.7, 41.0, 40.9, 40.5, 40.4, 37.7, 37.5, 29.8, 29.4, 28.3, 28.2, 28.1, 28.1, 27.9, 27.7, 27.7, 27.6, 26.5, 25.6, 25.4, 25.3, 25.2, 23.6, 23.4, 23.3; FT-IR ν: 2920, 2850, 1731, 1265, 1044, 735 cm－1; HRMS (ESI) calcd for C17H20Cl5INaO2 [M＋Na]＋ 580.8843, found 580.8841.
2-碘苯甲酸-6,7-二氯-3,7-二甲基辛酯(5): 无色液体, 产率94% (43 mg). 1H NMR (400 MHz, CDCl3) δ: 8.00~7.96 (m, 1H), 7.80~7.75 (m, 1H), 7.43~7.36 (m, 1H), 7.17~7.11 (m, 1H), 4.44~4.35 (m, 2H), 3.91~3.84 (m, 1H), 2.34~2.20 (m, 1H), 1.92~1.74 (m, 2H), 1.72~1.71 (m, 3H), 1.70~1.64 (m, 1H), 1.62~1.60 (m, 3H), 1.60~1.49 (m, 2H), 1.35~1.25 (m, 1H), 1.00 (t, J=7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 166.8, 141.4, 135.6, 132.6, 131.0, 128.0, 94.1, 72.1, 71.8, 71.4, 64.1, 35.8, 35.1, 34.9, 34.5, 31.9, 31.1, 30.9, 29.8, 29.4, 26.7, 19.9, 19.3; FT-IR ν: 2958, 2930, 1725, 1249, 1069, 705 cm－1; HRMS (ESI) calcd for C17H23Cl2INaO2 [M＋Na]＋ 479.0012, found 479.0010.
辅助材料(Supporting Information) 原料1a~1q、产物3~4和化合物5的1H NMR、13C NMR和19F NMR谱图. 这些材料可以免费从本刊网站(http://sioc-journal. cn/)上下载.
(Cheng, F.)