English

• α取代的1, 2-二氢喹啉和四氢喹啉是分布在活性天然产物和合成药物分子中的普遍性分子骨架, 具有抗生素、抗病毒、抗肿瘤和抗氧化等重要的生物活性^[1].因此, 开发经济、高效的方法来快速获得这一分子骨架是非常有意义的.目前最常采用的合成方案主要有以下两种.第一种是预先制备的α取代喹啉的催化氢化.该策略需在合成的早期引入α-取代基, 因此, 还原条件会限制α取代基的类型^[2].第二种是基于喹啉和酰氯产生的N-酰基亚胺正离子的亲核加成(Reissert型反应)^[3]或酸介导的2-乙氧基-1-乙氧碳酰基-1, 2-二氢喹啉类的缩醛分解反应^[4].由于α取代基可在合成后期通过一步反应引入到分子骨架中, 因此第二类反应为α取代二氢喹啉的合成提供了模块式的合成方法.其中, 1, 2-二氢喹啉与多种亲核试剂的直接氧化C—H官能化代表了一种更为经济和直观的方法, 它不需要事先安装活化基团, 因此在步骤经济和原子经济性方面均有着很好的优势^[5].

  过去几年来, N-杂环化合物的氧化C—H官能化受到了广泛的关注^[6].然而, N-杂环化合物的适用范围很大程度上局限于N-芳基保护的四氢异喹啉类化合物^[7].该方法后续芳基保护基的脱除需要在较为苛刻的反应条件下完成, 这一现状极大地限制了其在实际合成中的应用.此外, 适用于该方法的偶联试剂的类型较为有限^[8], 因此相应的杂环α取代形式的种类也较为局限.如果能实现N-酰基保护杂环的氧化碳氢官能化, 将可以很好地解决上述问题.然而, 与N-芳基保护的杂环相比, N-酰基保护杂环的活性以及相应中间体的稳定性均有较大程度的降低.因此, 对该类底物的氧化碳氢官能化被证明是更为困难的^[9]. 2014年, 刘磊等^[10]利用碳正离子Ph₃CClO₄作为氧化试剂, 实现了一系列N-酰基保护杂环与有机硼试剂的碳氢官能化.其中, 关于二氢喹啉的研究有三个例子, 是其与苄基硼试剂的氧化偶联(Scheme 1).考虑到有机硼试剂的广泛可适用性、良好的稳定性和独特的亲核性^[11], 我们在这里系统地报道了三苯基碳正离子介导的N-酰基二氢喹啉与类型多样的有机硼试剂的氧化C—H官能化反应.类型多样的炔基和烯基三氟硼酸钾均可与氧化体系兼容, 该模块式的反应允许快速构建在α位具有不同官能团模式的1, 2-二氢喹啉文库.

  图式 1

  

  图式 1.  Ph₃CClO₄介导的氧化碳氢官能化

  Scheme 1.  Oxidative C—H functionalization by Ph₃CClO₄

  下载: 全尺寸图片 幻灯片

  1.   结果与讨论

  1.1   反应条件的优化

  首先, 我们选用苯乙炔硼试剂作为亲核试剂, N-酰基1, 2-二氢喹啉(1a)作为底物建立一个反应模型, 来寻求氧化C-H炔基化合适的氧化条件(表 1, Entry 1~6).我们着重对三苯基碳正离子的阴离子效应进行了考察, 在室温条件下, 以苯乙炔硼试剂作为亲核试剂, 分别加入Ph₃CBF₄、Ph₃CPF₆、Ph₃CSbCl₆、Ph₃COTf和Ph₃CClO₄, 反应1 h后, 发现不同阴离子的三苯基碳正离子均能有所反应, 但同等条件下, 产率差距较大, 其中加入Ph₃CClO₄的反应体系能够以61%的产率获得目标产物, 而同等条件下, 不加入Ph₃CClO₄, 反应则不能进行.因此, 我们认为高氯酸根对三苯基碳正离子氧化该反应体系有着重要的促进作用, 但是目前对于具体的作用机制仍不清楚, 有待于进一步探索.

  表 1

  

  表 1  反应条件的优化^a

  Table 1.  Optimization of reaction conditions

  下载: 导出CSV

  Entry	Oxidant	Yieldb/%
  1	Ph3CBF4	26
  2	Ph3CPF6	24
  3	Ph3CSbCl6	32
  4	Ph3COTf	15
  5	Ph3CClO4	61
  6	―	＜5
  a Reaction conditions: 1a (0.1 mmol), 2 (0.15 mmol), 3 (0.1 mmol), CH2Cl2 (1.0 mL), 1 h, r.t. b Yield of isolated product.

  1.2   氧化碳氢炔基化和烯基化的范围

  在确定了碳正离子和亲核试剂的种类后, 我们对Ph₃CClO₄介导的氧化碳氢炔基化、烯基化和底物的适用范围进行了拓展(如表 2所示).选用1a作底物, 二氯甲烷(DCM)作溶剂, 在室温Ph₃CClO₄介导下, 利用广泛的有机硼炔试剂2对底物进行氧化碳氢官能化.无论是富含电子效应的芳炔基(3a~3f)还是直链烷炔基(3g~3i)的硼试剂, 均以61%~66%的产率获得目标产物, 表现出很好的兼容性.另外, 三甲基硅基(TMS)炔(3j)、氧苄基炔(3k)的硼试剂也能很好地进行反应.随后, 我们也证实了芳基烯(3l)和直链烷烯(3m)分别以54%和51%的产率获得目标产物.在证实了Ph₃CClO₄介导的氧化碳氢炔基化、烯基化范围后, 又对底物的电子效应进行了探索, 含有不同电子取代效应的N-酰基-1, 2-二氢喹啉1能够与芳基炔硼试剂较好地参与反应, 分别以62%~66%的产率获得了预期产物3n~3q.

  表 2

  

  表 2  Ph₃CClO₄介导的氧化碳氢炔基化、烯基化范围

  Table 2.  Scope of nucleophile and substrate by Ph₃CClO₄

  下载: 导出CSV

  2.   结论

  综上所述, 我们成功地实现了在Ph₃CClO₄介导下, N-酰基二氢喹啉与类型多样的有机硼试剂的氧化C—H官能化.该体系反应条件温和, 无需金属添加剂, 可简洁、模块化地实现N-酰基二氢喹啉α位的炔基化和烯基化.

  3.   实验部分

  3.1   仪器与试剂

  氢谱(¹H NMR)和碳谱(¹³C NMR)均在Bruker Avance DRX 500型核磁共振波谱仪上测定, CDCl₃为溶剂, TMS为内标; 柱层析所用硅胶为200~300目和薄层层析法(TCL)检测所用的硅胶板型号为GF254, 均购买自青岛海洋化工有限公司.质谱数据均采用美国Agilent Q-TOF 6510型高分辨质谱仪测定.

  实验所需试剂均购买自安耐吉试剂公司、麦克林试剂公司和柏卡试剂公司等.实验所需溶剂, 如二氯甲烷、石油醚、乙酸乙酯等常用溶剂, 均购自于购自天津富宇精细化工有限公司, 使用前均按相关文献进行标准纯化处理.

  3.2   实验方法

  向含有二氯甲烷(1.0 mL)中加入N-氨基甲酰基-1, 2-二氢喹啉1 (0.1 mmol)、有机硼试剂2 (0.15 mmol)和Ph₃CClO₄ (0.1 mmol)于圆底烧瓶中.加N₂气球保护, 在室温下, 置于磁力搅拌器上进行搅拌反应1 h, 直至通过薄层色谱(TLC)监测所有N-氨基甲酰基-1, 2-二氢喹啉消失.反应停止后, 然后低温减压除去挥发物, 残余物通过硅胶色谱柱进行柱层析纯化, 用乙酸乙酯/石油醚作为洗脱剂, 得到所需产物.

  2-(苯基乙炔基)-1, 2-二氢萘-1-羧酸甲酯(3a)^[6g]:无色液体, 产率61%. ¹H NMR (500 MHz, CDCl₃) δ: 7.66 (s, 1H), 7.30~7.19 (m, 6H), 7.17~7.08 (m, 2H), 6.58 (dt, J＝7.9, 3.8 Hz, 1H), 6.12 (d, J＝5.5 Hz, 2H), 3.87 (s, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 154.51, 134.39, 132.00, 128.51, 128.27, 128.07, 126.81, 126.10, 125.35, 124.76, 124.49, 122.63, 85.72, 83.71, 53.58, 44.91; HRMS (ESI) calcd for C₁₉H₁₆NO₂ [M+H]⁺ 290.1103, found 290.1100.

  2-(对甲苯基乙炔基)-1, 2-二氢萘-1-羧酸甲酯(3b)^[6g]:无色液体, 产率65%. ¹H NMR (500 MHz, CDCl₃) δ: 7.58 (s, 1H), 7.18 (d, J＝14.9 Hz, 1H), 7. 11 (d, J＝7.9 Hz, 2H), 7.05 (dt, J＝14.4, 7.0 Hz, 2H), 6.95 (d, J＝7.8 Hz, 2H), 6.48 (d, J＝7.8 Hz, 1H), 6.07~5.96 (m, 2H), 3.78 (s, 3H), 2.21 (s, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 153.33, 137.20, 133.22, 130.69, 127.81, 126.82, 125.57, 124.77, 124.28, 123.51, 123.30, 118.35, 83.77, 82.64, 52.36, 43.75, 28.65, 20.40; HRMS (ESI) calcd for C₂₀H₁₈NO₂ [M+H]⁺304.1259, found 304.1278.

  2-(间甲苯基乙炔基)-1, 2-二氢萘-1-羧酸甲酯(3c)^[6g]:无色液体, 产率62%. ¹H NMR (500 MHz, CDCl₃) δ: 7.57 (s, 1H), 7.21~7.15 (m, 1H), 7.06~7.02 (m, 5H), 6.99~6.94 (m, 1H), 6.48 (q, J＝4.3 Hz, 1H), 6.10~5.90 (m, 2H), 3.78 (s, 3H), 2.17 (s, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 153.30, 136.74, 133.20, 131.37, 128.19, 127.86, 126.96, 126.84, 125.59, 124.83, 124.19, 123.53, 123.29, 121.21, 84.12, 82.65, 52.36, 43.72, 20.07; HRMS (ESI) calcd for C₂₀H₁₈NO₂ [M+H]⁺ 304.1259, found 304.1289.

  2-[(4-甲氧基苯基)乙炔基]-1, 2-二氢萘-1-羧酸甲酯(3d)^[6g]:无色液体, 产率66%. ¹H NMR (500 MHz, CDCl₃) δ: 7.57 (s, 1H), 7.20~7.12 (m, 3H), 7.09~6.99 (m, 2H), 6.66 (d, J＝8.7 Hz, 2H), 6.47 (d, J＝8.2 Hz, 1H), 6.06~5.95 (m, 2H), 3.77 (s, 3H), 3.67 (s, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 158.48, 153.24, 133.11, 132.17, 126.70, 125.52, 125.46, 124.58, 124.25, 123.39, 123.20, 113.42, 112.58, 82.98, 82.32, 54.09, 52.24, 43.67; HRMS (ESI) calcd for C₂₀H₁₇NO₃ [M+H]⁺ 320.1208, found 320.1298.

  2-[(4-氯苯基)乙炔基]-1, 2-二氢萘-1-羧酸甲酯(3e)^[6g]:无色液体, 产率62%. ¹H NMR (500 MHz, CDCl₃) δ: 7.56 (s, 1H), 7.20~7.16 (m, 1H), 7.14~7.08 (m, 4H), 7.08~7.01 (m, 2H), 6.51~6.45 (m, 1H), 6.06~5.96 (m, 2H), 3.77 (s, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 154.49, 134.56, 134.32, 133.24, 128.61, 128.14, 126.85, 126.71, 126.25, 124.81, 124.47, 121.13, 86.75, 82.58, 53.62, 44.86; HRMS (ESI) calcd for C₁₉H₁₅ClNO₂ [M+ H]⁺ 324.0713, found 324.0840.

  2-[(4-溴苯基)乙炔基]-1, 2-二氢萘-1-羧酸甲酯(3f)^[6g]:无色液体, 产率64%. ¹H NMR (500 MHz, CDCl₃) δ: 7.66 (s, 1H), 7.38~7.34 (m, 2H), 7.30~7.25 (m, 1H), 7.18~7.11 (m, 4H), 6.58 (q, J＝4.4 Hz, 1H), 6.14~6.04 (m, 2H), 3.87 (s, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 154.48, 134.32, 133.45, 131.54, 128.14, 126.86, 126.71, 126.27, 125.01, 124.82, 124.47, 122.80, 121.60, 86.95, 82.65, 53.63, 44.88; HRMS (ESI) calcd for C₁₉H₁₅BrNO₂ [M+H]⁺ 368.0208, found 368.0333.

  2-(己-1-炔-1-基)-1, 2-二氢萘-1-羧酸甲酯(3g)^[6g]:无色液体, 产率63%. ¹H NMR (500 MHz, CDCl₃) δ: 7.54 (s, 1H), 7.19~7.14 (m, 1H), 7.07~6.97 (m, 2H), 6.42 (d, J＝9.3 Hz, 1H), 5.96 (dd, J＝9.3, 6.2 Hz, 1H), 5.75 (s, 1H), 3.75 (s, 3H), 1.98 (td, J＝7.1, 2.0 Hz, 2H), 1.30~1.24 (m, 2H), 1.17~1.11 (m, 2H), 0. 72 (t, J＝7.3 Hz, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 153.29, 133.28, 126.66, 125.72, 125.44, 125.13, 124.22, 123.41, 123.28, 83.49, 75.35, 52.25, 43.36, 29.44, 20.68, 17.38, 12.48; HRMS (ESI) calcd for C₁₇H₂₀NO₂ [M+H]⁺ 270.1416, found 270.1572.

  2-(辛-1-炔-1-基)-1, 2-二氢萘-1-羧酸甲酯(3h)^[6g]:无色液体, 产率65%. ¹H NMR (500 MHz, CDCl₃) δ: 7.53 (s, 1H), 7.16~7.11 (m, 1H), 7.02~6.96 (m, 2H), 6. 39 (d, J＝9.3 Hz, 1H), 5. 93 (dd, J＝9.3, 6.2 Hz, 1H), 5.74 (s, 1H), 3.72 (s, 3H), 1.95 (td, J＝7.1, 2.0 Hz, 2H), 1.29~1.21 (m, 2H), 1.16~1.03 (m, 6H), 0.75 (t, J＝7.1 Hz, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 153.32, 133.36, 126.75, 125.77, 125.52, 125.14, 124.29, 123.47, 123.31, 83.55, 75.49, 52.28, 43.44, 30.25, 27.38, 27.29, 21.52, 17.74, 13.06; HRMS (ESI) calcd for C₁₉H₂₄NO₂ [M+H]⁺ 298.1729, found 298.1864.

  2-(癸-1-炔-1-基)-1, 2-二氢萘-1-羧酸甲酯(3i)^[6g]:无色液体, 产率62%. ¹H NMR (500 MHz, CDCl₃) δ: 7.54 (s, 1H), 7.18~7.15 (m, 1H), 7.04~7.02 (m, 2H), 6.42 (d, J＝9.3 Hz, 1H), 5.96 (dd, J＝9.2, 6.3 Hz, 1H), 5.75 (s, 1H), 3.75 (s, 3H), 1.97 (td, J＝7.1, 1.8 Hz, 2H), 1.27 (dd, J＝13.8, 6.8 Hz, 2H), 1.21~1.18 (m, 2H), 1.11~1.10 (m, 8H), 0.80 (t, J＝7.1 Hz, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 153.28, 133.27, 126.68, 125.71, 125.44, 125.09, 124.21, 123.41, 123.25, 83.54, 75.34, 52.25, 43.35, 30.78, 28.10, 27.96, 27.58, 27.36, 21.63, 17.68, 13.08; HRMS (ESI) calcd for C₂₁H₂₈NO₂ [M+H]⁺ 326.2042, found 326.2207.

  2-[(三甲基甲硅烷基)乙炔基]-1, 2-二氢萘-1-羧酸甲酯(3j)^[6g]:无色液体, 产率60%. ¹H NMR (500 MHz, CDCl₃) δ: 7.61 (s, 1H), 7.28~7.24 (m, 1H), 7.14~711 (m, 2H), 6.52 (d, J＝9.3 Hz, 1H), 6.03 (dd, J＝9.3, 6.2 Hz, 1H), 5.87 (d, J＝5.8 Hz, 1H), 3.84 (s, 3H), 0.05 (s, 9H); ¹³C NMR (126 MHz, CDCl₃) δ: 154.48, 134.38, 127.96, 126.84, 126.72, 125.99, 125.52, 124.72, 124.59, 101.79, 88.65, 53.55, 45.05, 0.00; HRMS (ESI) calcd for C₁₆H₂₀NO₂Si [M+H]⁺ 286.1185, found 286.1313.

  2-[4-(苄氧基)丁-1-炔-1-基]-1, 2-二氢萘-1-甲酸甲酯(3k)^[6g]:无色液体, 产率67%. ¹H NMR (500 MHz, CDCl₃) δ: 7.53 (s, 1H), 7.28~7.22 (m, 2H), 7.21~7.12 (m, 4H), 7.06~6.96 (m, 2H), 6.42 (d, J＝9.3 Hz, 1H), 5.94 (dd, J＝9.3, 6.2 Hz, 1H), 5.78 (s, 1H), 4.37 (s, 2H), 3.74 (s, 3H), 3.38 (t, J＝7.0 Hz, 2H), 2.31 (td, J＝7.0, 2.1 Hz, 2H); ¹³C NMR (126 MHz, CDCl₃) δ: 154.47, 138.27, 134.35, 128.59, 128.54, 127.95, 127.87, 127.80, 126.76, 126.71, 125.57, 124.66, 124.43, 81.12, 77.68, 73.07, 68.35, 53.49, 44.47, 20.42; HRMS (ESI) calcd for C₂₂H₂₂NO₃ [M+H]⁺ 348.1521, found 348.1543.

  (E)-2-苯乙烯基-1, 2-二氢萘-1-羧酸甲酯(3l)^[6g]:无色液体, 产率54%. ¹H NMR (500 MHz, CDCl₃) δ: 7.52 (s, 1H), 7.22~7.06 (m, 6H), 6.99 (dt, J＝14.7, 7.3 Hz, 2H), 6.46 (dd, J＝23.6, 12.7 Hz, 2H), 6.03~5.90 (m, 2H), 5.62 (s, 1H), 3.76 (s, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 154.01, 135.65, 133.74, 130.70, 127.64, 126.95, 126.87, 126.35, 126.15, 125.75, 125.63, 124.80, 124.67, 123.51, 123.43, 53.55, 52.35; HRMS (ESI) calcd for C₁₉H₁₈NO₂ [M+H]⁺ 292.1259, found 292.1326.

  (E)-2-(癸-1-烯-1-基)-1, 2-二氢萘-1-甲酸甲酯(3m)^[6g]:无色液体, 产率51%. ¹H NMR (500 MHz, CDCl₃) δ: 7.49 (s, 1H), 7.14~7.06 (m, 1H), 7.04~6.89 (m, 2H), 6.41 (d, J＝9.5 Hz, 1H), 5.90 (dd, J＝9.4, 6.1 Hz, 1H), 5.59~5.47 (m, 1H), 5.39 (s, 1H), 5.27~5.17 (m, 1H), 3.74 (s, 3H), 1.83 (dt, J＝13.6, 6.8 Hz, 2H), 1.18~1.02 (m, 12H), 0.80 (t, J＝7.0 Hz, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 153.91, 133.76, 132.53, 127.31, 126.53, 126.28, 125.32, 124.77, 124.04, 123.44, 123.18, 53.32, 52.12, 31.18, 30.96, 28.46, 28.33, 28.05, 28.01, 21.78, 13.22; HRMS (ESI) calcd for C₂₁H₃₀NO₂ [M+H]⁺328.2198, found 328.2395.

  6-甲基-2-(苯基乙炔基)喹啉-1(2H)-甲酸甲酯(3n)^[6g]:无色液体, 产率62%. ¹H NMR (500 MHz, CDCl₃) δ: 7.45 (s, 1H), 7.24~7.19 (m, 2H), 7.17~7.08 (m, 3H), 6.99 (d, J＝8.2 Hz, 1H), 6.88 (s, 1H), 6.45 (dt, J＝7.7, 3.7 Hz, 1H), 6.01 (d, J＝5.3 Hz, 2H), 3.77 (s, 3H), 2.25 (s, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 153.13, 133.12, 130.81, 130.65, 127.53, 127.25, 127.04, 126.09, 125.43, 124.94, 123.12, 121.50, 84.62, 82.37, 52.32, 43.74, 19.81; HRMS (ESI) calcd for C₂₀H₁₈NO₂ [M+H]⁺304.1259, found 304.1317.

  7-甲基-2-(苯基乙炔基)喹啉-1(2H)-甲酸甲酯(3o)^[6g]:无色液体, 产率64%. ¹H NMR (500 MHz, CDCl₃) δ: 7.41 (s, 1H), 7.25~7.21 (m, 2H), 7.17~7.14 (m, 3H), 6.95 (d, J＝7.7 Hz, 1H), 6. 85 (d, J＝7.7 Hz, 1H), 6.46 (d, J＝9.1 Hz, 1H), 5.97 (dt, J＝9.0, 6.0 Hz, 2H), 3.78 (s, 3H), 2.29 (s, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 153.47, 137.06, 133.20, 130.97, 127.41, 127.19, 125.53, 124.94, 124.53, 123.94, 123.14, 121.65, 84.90, 82.40, 52.50, 43.88, 20.84; HRMS (ESI) calcd for C₂₀H₁₈NO₂ [M+H]⁺ 304.1259, found 304.1285.

  6-氯-2-(苯基乙炔基)喹啉-1(2H)-甲酸甲酯(3p)^[6g]:淡黄色液体, 产率63%. ¹H NMR (500 MHz, CDCl₃) δ: 7.54 (s, 1H), 7.23 (dd, J＝7.9, 1.6 Hz, 2H), 7.19~7.13 (m, 4H), 7.06 (d, J＝2.4 Hz, 1H), 6.43 (d, J＝9.2 Hz, 1H), 6.09 (dd, J＝9.2, 6.3 Hz, 1H), 6.02 (s, 1H), 3.79 (s, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 153.05, 131.71, 130.81, 128.69, 127.46, 127.11, 127.04, 126.69, 125.50, 125.22, 124.58, 123.96, 121.22, 83.92, 82.91, 52.53, 43.71; HRMS (ESI) calcd for C₁₉H₁₅ClNO₂ [M+H]⁺ 324.0713, found 324.0810.

  4, 7-二氯-2-(苯基乙炔基)喹啉-1(2H)-甲酸甲酯(3q)^[6g]:淡黄色液体, 产率66%. ¹H NMR (500 MHz, CDCl₃) δ: 7.64 (s, 1H), 7.50 (d, J＝8.4 Hz, 1H), 7.24~7.18 (m, 4H), 7.17~7.14 (m, 1H), 7.12 (dd, J＝8.4, 2.0 Hz, 1H), 6.17 (d, J＝6.8 Hz, 1H), 6. 07 (d, J＝6.6 Hz, 1H), 3.82 (s, 3H); ¹³C NMR (126 MHz, CDCl₃) δ: 152.56, 134.50, 133.84, 130.85, 128.35, 127.68, 127.17, 124.85, 123.87, 123.35, 122.56, 121.29, 120.88, 83.60, 82.79, 52.84, 44.63; HRMS (ESI) calcd for C₁₉H₁₄Cl₂NO₂ [M+H]⁺ 358.0323, found 358.0317.

  辅助材料(Supporting Information)  产物3a~3n的核磁共振图谱.这些材料可以免费从本刊网站(http://siocjournal.cn/)上下载.

• 1. [1]

     (a) Michael, J. P. Nat. Prod. Rep. 2007, 24, 223.
     (b) Michael, J. P. Nat. Prod. Rep. 2008, 25, 166.
     (c) Welsch, M. E. ; Snyder, S. A. ; Stockwell, B. R. Curr. Opin. Chem. Biol. 2010, 14, 347.

  2. [2]

     (a) Kouznetsov, V. ; Palma, A. ; Ewert, C. ; Varlamov, A. J. Heterocycl. Chem. 1998, 35, 761.
     (b) Sridharan, V. ; Suryavanshi, P. A. ; Menéndez, J. C. Chem. Rev. 2011, 111, 7157.
     (c) Katritzky, A. R. ; Rachwal, S. ; Rachwal, B. Tetrahedron 1996, 52, 15031.

  3. [3]

     (a) Takamura, M. ; Funabashi, K. ; Kanai, M. ; M. Shibasaki, J. Am. Chem. Soc. 2001, 123, 6801.
     (b) Yamaoka, Y. ; Miyabe, H. ; Takemoto, Y. J. Am. Chem. Soc. 2007, 129, 6686.

  4. [4]

     (a) Graham, T. J. A. ; Shields, J. D. ; Doyle, A. G. Chem. Sci. 2011, 2, 980.
     (b) Kodama, T. ; Moquist, P. N. ; Schaus, S. E. Org. Lett. 2011, 13, 6316.
     (c) Sun, S. ; Mao, Y. ; Lou, H. ; Liu, L. Chem. Commun. 2015, 51, 10691.
     (d) Volla, C. M. R. ; Fava, E. ; Atodiresei, L. ; Rueping, M. Chem. Commun. 2015, 51, 15788.
     (e) Berti, F. ; Malossi, F. ; Marchettib, F. ; Pineschi, M. Chem. Commun. 2015, 51, 13694.

  5. [5]

     (a) Trost, B. M. Acc. Chem. Res. 2002, 35, 695.
     (b) Wender, P. A. ; Verma, V. A. ; Paxton, T. J. ; Pillow, T. H. Acc. Chem. Res. 2008, 41, 40.

  6. [6]

     (a) Murahashi, S. ; Zhang, D. Chem. Soc. Rev. 2008, 37, 1490.
     (b) Liu, C. ; Zhang, H. ; Shi, W. ; Lei, A. Chem. Rev. 2011, 111, 1780.
     (c) Li, C. J. Acc. Chem. Res. 2009, 42, 335.
     (d) Sun, C. L. ; Li, B. J. ; Shi, Z. J. Chem. Rev. 2011, 111, 1293.
     (e) Zhang, C. ; Tang, C. ; Jiao, N. Chem. Soc. Rev. 2012, 41, 3464.
     (f) Cho, S. H. ; Kim, J. Y. ; Kwak, J. ; Chang, S. Chem. Soc. Rev. 2011, 40, 5068.
     (g) Liu, Z. ; Chen, L. ; Li, J. ; Liu, K. ; Zhao, J. ; Xu, M. ; Feng, L. ; Wan, R. ; Li, W. ; Liu, L. Org. Biomol. Chem, 2017, 15, 7600.
     (h) Yeung, C. S. ; Dong, V. M. Chem. Rev. 2011, 111, 1215.
     (i) Liu, X. ; Sun, S. ; Meng, Z. ; Lou, H. ; Liu, L. Org. Lett. 2015, 17, 2396.
     (j) Xie, Z. ; Zan, X. ; Sun, S. ; Pan, X. ; Liu, L. Org. Lett. 2016, 18, 3944.
     (k)Wang, G., Mao, Y., Liu, L. Org. Lett. 2016, 18, 6476.
     (l) Zhang, Q. ; Lv, J. ; Luo, S. Acta Chim. Sinica 2016, 74, 61(in Chinese).
     (张启超, 吕健, 罗三中, 化学学报, 2016, 74, 61. )
     (m) Qin, Y. ; Zhu, L. ; Luo, S. Chem. Rev. 2017, 117, 9433.

  7. [7]

     (a) Murahashi, S. -I. ; Komiya, N. ; Terai, H. ; Nakae, T. J. Am. Chem. Soc. 2003, 125, 15312.
     (b) Murahashi, S. -I. ; Nakae, T. ; Terai, H. ; Komiya, N. J. Am. Chem. Soc. 2008, 130, 11005.
     (c) Boess, E. ; Sureshkumar, D. ; Sud, A. ; Wirtz, C. ; Farès, C. ; Klussmann, M. J. Am. Chem. Soc. 2011, 133, 8106.
     (d) Boess, E. ; Schmitz, C. ; Klussmann, M. J. Am. Chem. Soc. 2012, 134, 5317.
     (e) Li, Z. ; Li, C. J. J. Am. Chem. Soc. 2004, 126, 11810.
     (f) Li, Z. ; Yu, R. ; Li, H. Angew. Chem., Int. Ed. 2008, 47, 7497.
     (g) Yang, F. ; Li, J. ; Xie, J. ; Huang, Z. Z. Org. Lett. 2010, 12, 5214.
     (h) Muramatsu, W. ; Nakano, K. ; Li, C. J. Org. Lett. 2013, 15, 3650.
     (i) Li, Z. ; Li, C. -J. Org. Lett. 2004, 6, 4997.
     (j) Zhang, G. ; Zhang, Y. ; Wang, R. Angew. Chem., Int. Ed. 2011, 50, 10429.

  8. [8]

     (a) Guo, C. ; Song, J. ; Luo, S. -W. ; Gong, L. -Z. Angew. Chem., Int. Ed. 2010, 49, 5558.
     (b) Li, Z. ; MacLeod, P. D. ; Li, C. -J. Tetrahedron: Asymmetry 2006, 17, 590.
     (c) Yang, Q. ; Zhang, L. ; Ye, C. ; Luo, S. ; Wu, L. -Z. Tung, C. -H. Angew. Chem., Int. Ed. 2017, 56, 3694.
     (d) Neel, A. J. ; Hehn, J. P. ; Tripet, P. F. ; Toste, F. D. J. Am. Chem. Soc. 2013, 135, 14044.
     (e) Zhang, G. ; Ma, Y. ; Wang, S. ; Zhang, Y. ; Wang, R. J. Am. Chem. Soc. 2012, 134, 12334.
     (f) Zhang, G. ; Ma, Y. ; Wang, S. ; Kong, W. ; Wang, R. Chem. Sci. 2013, 4, 2645.
     (g) Bergonzini, G. ; Schindler, C. S. ; Wallentin, C. -J. ; Jacobsen, E. N. ; Stephenson, C. R. J. Chem. Sci. 2014, 5, 112.

  9. [9]

     (a) Pintér, Á . ; Sud, A. ; Sureshkumar, D. ; Klussmann, M. Angew. Chem., Int. Ed. 2010, 49, 5004.
     (b) Liu, X. ; Meng, Z. ; Li, C. ; Lou, H. ; Liu, L. Angew. Chem., Int. Ed. 2015, 54, 6012.
     (c) Richter, H. ; Frö hlich, R. ; Daniliuc, C. -G. ; García Mancheñ o, O. Angew. Chem., Int. Ed. 2012, 51, 8656.
     (d) Richter, H. ; García Mancheñ o, O. Eur. J. Org. Chem. 2010, 4460.
     (e) Ghobrial, M. ; Harhammer, K. ; Mihovilovic, M. D. ; Schnürch, M. Chem. Commun. 2010, 46, 8836.
     (f) Ghobrial, M. ; Schnürch, M. ; Mihovilovic, M. D. J. Org. Chem. 2011, 76, 8781.
     (g) Liu, X. ; Sun, B. ; Xie, Z. ; Qin, X. ; Liu, L. ; Lou, H. J. Org. Chem. 2013, 78, 3104.
     (h) Sun, S. ; Li, C. ; Floreancig, P. E. ; Lou, H. ; Liu, L. Org. Lett. 2015, 17, 1684.
     (i) Long, H. ; Wang, G. ; Lu, R. ; Xu, M. ; Zhang, K. ; Qi, S. ; He, Y. ; Bu, Y. ; Liu, L. Org. Lett. 2017, 19, 2146.

  10. [10]

      (a) Xie, Z. ; Liu, L. ; Chen, W. ; Zheng, H. ; Xu, Q. ; Yuan, H. ; Lou, H. Angew. Chem., Int. Ed. 2014, 53, 3904.
      (b) Chen, W. ; Xie, Z. ; Zheng, H. ; Lou, H. ; Liu, L. Org. Lett. 2014, 16, 5988.
      (c) Wan, M. ; Meng, Z. ; Lou, H. ; Liu, L. Angew. Chem., Int. Ed. 2014, 53, 13845.

  11. [11]

      (a) Kim, H. ; MacMillan, D. W. C. J. Am. Chem. Soc. 2008, 130, 398.
      (b) Vo, C. -V. T. ; Mitchell, T. A. ; Bode, J. W. J. Am. Chem. Soc. 2011, 133, 14082.
      (c) Fujiwara, Y. ; Domingo, V. ; Seiple, I. B. ; Gianatassio, R. ; Del Bel, M. ; Baran, P. S. J. Am. Chem. Soc. 2011, 133, 3292.
      (d) Nielsen, D. K. ; Doyle, A. G. Angew. Chem., Int. Ed. 2011, 50, 6056.

• 

  图式 1  Ph₃CClO₄介导的氧化碳氢官能化

  Scheme 1  Oxidative C—H functionalization by Ph₃CClO₄

  下载: 全尺寸图片 幻灯片

  表 1  反应条件的优化^a

  Table 1.  Optimization of reaction conditions

  Entry	Oxidant	Yieldb/%
  1	Ph3CBF4	26
  2	Ph3CPF6	24
  3	Ph3CSbCl6	32
  4	Ph3COTf	15
  5	Ph3CClO4	61
  6	―	＜5
  a Reaction conditions: 1a (0.1 mmol), 2 (0.15 mmol), 3 (0.1 mmol), CH2Cl2 (1.0 mL), 1 h, r.t. b Yield of isolated product.

  下载: 导出CSV

  表 2  Ph₃CClO₄介导的氧化碳氢炔基化、烯基化范围

  Table 2.  Scope of nucleophile and substrate by Ph₃CClO₄

  下载: 导出CSV
•