以7b-甲基-1,1a,2,7b-四氢环丙[c]苯并呋喃(2)的合成为例. 在干燥的10 mL平底高硼硅样品瓶中, 依次加入N-对甲苯磺酰腙底物(0.2 mmol, 1.0 equiv.)和无水碳酸铯(Cs2CO3, 195 mg, 0.6 mmol, 3.0 equiv.). 将体系抽真空并用氮气置换三次. 在氩气氛围下, 加入甲苯(1.0 mL). 随后, 将反应管置于385 nm LED平行反应仪上, 于室温(25 ℃)下搅拌反应20 h. 反应情况通过薄层色谱(TLC)监测. 反应结束后, 将反应液过滤、减压浓缩. 所得粗产物通过硅胶柱层析[洗脱剂: 纯石油醚、石油醚/乙酸乙酯(V∶V =10∶1)]纯化, 得到目标的杂环化合物产物.
7b-甲基-1,1a,2,7b-四氢环丙[c]苯并呋喃(2): 27.2 mg, 无色油状液体, dr 1∶1, 产率85%. 1H NMR (400 MHz, Chloroform-d) δ: 7.37 (dd, J=7.6, 1.6 Hz, 1H), 7.08 (td, J=7.6, 1.6 Hz, 1H), 6.96 (td, J=7.6, 1.2 Hz, 1H), 6.82 (dd, J=8.0, 1.2 Hz, 1H), 4.28 (dd, J=10.4, 1.2 Hz, 1H), 3.92 (dd, J=10.4, 1.2 Hz, 1H), 1.51~1.47 (m, 4H), 1.18 (t, J=4.8 Hz, 1H), 0.88 (dd, J=8.2, 4.6 Hz, 1H); 13C NMR (101 MHz, Chloroform-d) δ: 152.3, 130.8, 125.9, 125.7, 121.4, 117.0, 62.6, 26.2, 21.9, 16.7, 15.2; HRMS (ESI) calcd for C11H13O [M+H]+ 161.0966, found 161.0967.
5-氟-7b-甲基-1,1a,2,7b-四氢环丙[c]色烯(3): 28 mg, 无色油状液体, dr 1∶1, 产率79%. 1H NMR (400 MHz, Chloroform-d) δ: 7.27~7.24 (m, 1H), 6.65 (td, J=8.4, 2.8 Hz, 1H), 6.54 (dd, J=10.0, 2.8 Hz, 1H), 4.27 (d, J=10.4 Hz, 1H), 3.91 (d, J=10.8 Hz, 1H), 1.47~1.42 (m, 4H), 1.07 (t, J=5.0 Hz, 1H), 0.86~0.83 (m, 1H); 13C NMR (101 MHz, Chloroform-d) δ: 161.1 (d, J=243.8 Hz), 153.2 (d, J=11.6 Hz), 126.4 (d, J=3.0 Hz), 126.3 (d, J=9.4 Hz), 108.0 (d, J=21.1 Hz), 104.6 (d, J=24.0 Hz), 63.1, 25.5, 22.0, 16.7, 14.8; HRMS (ESI) calcd for C11H12FO [M+H]+ 179.0872, found 179.0874.
5-溴-7b-甲基-1,1a,2,7b-四氢环丙[c]香豆素(4): 37 mg, 无色油状液体, dr 1∶1, 产率64%. 1H NMR (600 MHz, Chloroform-d) δ: 7.20 (d, J=8.4 Hz, 1H), 7.06 (d, J=8.4 Hz, 1H), 6.97 (s, 1H), 4.27 (d, J=10.2 Hz, 1H), 3.90 (d, J=10.8 Hz, 1H), 1.49~1.47 (m, 4H), 1.13 (t, J=5.4 Hz, 1H), 0.89~0.87 (m, 1H); 13C NMR (151 MHz, Chloroform-d) δ: 153.9, 129.9, 127.0, 124.3, 120.2, 118.6, 62.9, 25.9, 21.7, 16.8, 15.1; HRMS (ESI) calcd for C11H12- BrO [M+H]+ 239.0072, found 239.0076.
6-溴-7b-甲基-1,1a,2,7b-四氢环丙[c]香豆素(5): 39 mg, 无色油状液体, dr 1∶1, 产率68%. 1H NMR (400 MHz, Chloroform-d) δ: 7.43 (d, J=2.4 Hz, 1H), 7.15 (dd, J=8.8, 2.4 Hz, 1H), 6.67 (d, J=8.4 Hz, 1H), 4.27 (d, J=10.4 Hz, 1H), 3.87 (d, J=10.4 Hz, 1H), 1.51~1.47 (m, 4H), 1.15 (t, J=5.0 Hz, 1H), 0.90~0.87 (m, 1H); 13C NMR (101 MHz, Chloroform-d) δ: 151.4, 133.1, 128.7, 128.6, 118.7, 113.7, 62.7, 26.1, 21.7, 16.9, 15.3; HRMS (ESI) calcd for C11H12BrO [M+H]+ 239.0072, found 239.0069.
N-(7b-甲基-1,1a,2,7b-四氢环丙[c]色烯-6-基)乙酰胺(6): 23.4 mg, 无色油状液体, dr 1∶1, 产率54%. 1H NMR (400 MHz, Chloroform-d) δ: 7.54 (s, 1H), 7.49 (d, J=2.4 Hz, 1H), 7.10 (dd, J=8.6, 2.6 Hz, 1H), 6.72 (d, J=8.4 Hz, 1H), 4.23 (d, J=10.4 Hz, 1H), 3.84 (d, J=10.4 Hz, 1H), 2.13 (s, 3H), 1.46~1.44 (s, 4H), 1.13 (t, J=5.0 Hz, 1H), 0.84 (dd, J=8.2, 4.6 Hz, 1H); 13C NMR (101 MHz, Chloroform-d) δ: 168.4, 149.1, 131.6, 131.2, 118.6, 118.5, 117.0, 62.7, 26.0, 24.3, 21.8, 16.7, 15.4; HRMS (ESI) calcd for C13H16NO2 [M+H]+ 218.1181, found 218.1184.
7b-甲基-1a,2,3,7b-四氢-1H-环丙[c]喹啉(7): 15 mg, 无色油状液体, dr 1∶1, 产率47%. 1H NMR (400 MHz, Chloroform-d) δ: 7.31 (dd, J=7.6, 1.6 Hz, 1H), 6.97 (td, J=7.6, 1.2 Hz, 1H), 6.75 (td, J=7.6, 1.2 Hz, 1H), 6.49 (dd, J=8.0, 1.2 Hz, 1H), 3.33 (d, J=1.6 Hz, 2H), 1.48~1.43 (m, 5H), 0.70~0.65 (m, 1H); 13C NMR (101 MHz, Chloroform-d) δ: 142.4, 128.9, 125.8, 125.5, 118.2, 114.1, 38.9, 27.0, 22.9, 15.9, 14.3; HRMS (ESI) calcd for C11H14- N [M+H]+ 160.1126, found 160.1125.
6-氯-7b-苯基-1a,2,3,7b-四氢-1H-环丙[c]喹啉(8): 21 mg, 无色油状液体, dr 1∶1, 产率41%. 1H NMR (600 MHz, Chloroform-d) δ: 7.39~7.26 (m, 4H), 7.31~7.28 (m, 1H), 6.87 (dd, J=8.4, 2.4 Hz, 1H), 6.59 (d, J=2.4 Hz, 1H), 6.44 (d, J=8.4 Hz, 1H), 3.69 (s, 1H), 3.48 (d, J=2.4 Hz, 2H), 1.82~1.80 (m, 1H), 1.72 (t, J=5.1 Hz, 1H), 1.40 (dd, J=8.4, 4.8 Hz, 1H); 13C NMR (151 MHz, Chloroform-d) δ: 143.5, 140.9, 130.5, 130.2, 128.6, 128.3, 126.9, 125.5, 122.7, 115.2, 38.8, 27.4, 27.0, 13.6; HRMS (ESI) calcd for C16H15ClN [M+H]+ 256.0873, found 256.0876.
2-(1-溴乙烯基)-3-甲基-2,3-二氢苯并呋喃(9): 36 mg, 无色油状液体, dr 1∶1, 产率76%. 1H NMR (400 MHz, Chloroform-d) δ: 7.16~7.13 (m, 2H), 6.91 (td, J=7.4, 1.0 Hz, 1H), 6.84 (d, J=8.0 Hz, 1H), 6.02 (dd, J=1.8, 1.0 Hz, 1H), 5.62 (d, J=2.0 Hz, 1H), 4.72 (d, J=6.4 Hz, 1H), 3.53 (p, J=6.8 Hz, 1H), 1.43 (d, J=7.2 Hz, 3H); 13C NMR (101 MHz, Chloroform-d) δ: 158.5, 131.9, 130.8, 128.3, 123.9, 121.1, 117.8, 109.4, 92.0, 42.6, 19.9; HRMS (ESI) calcd for C11H12BrO [M+H]+ 239.0072, found 239.0071.
2-(丁-3-烯-1-基)-3-甲基-2,3-二氢苯并呋喃(10): 27.0 mg, 无色油状液体, dr 6.8∶1, 产率72%. 1H NMR (400 MHz, Chloroform-d) δ: 7.17~7.11 (m, 2H), 6.87 (t, J=7.2 Hz, 1H), 6.79 (d, J=8.4 Hz, 1H), 5.95~5.85 (m, 1H), 5.14~5.02 (m, 2H), 4.71~4.65 (m, 0.18H), 4.31~4.26 (m, 1H), 3.44~3.37 (m, 0.18H), 3.20~3.12 (m, 0.82H), 2.41~2.22 (m, 2H), 1.95~1.69 (m, 2H), 1.34 (d, J=6.8 Hz, 2H), 1.19 (d, J=7.2 Hz, 1H); 13C NMR (101 MHz, Chloroform-d) δ: 159.1, 158.6, 138.0, 137.9, 133.4, 132.3, 128.0, 127.9, 124.0, 123.7, 120.3, 120.2, 115.1, 115.0, 109.4, 109.3, 90.3, 85.7, 42.1, 38.9, 34.3, 30.6, 29.8, 29.2, 19.0, 15.1; HRMS (ESI) calcd for C13H17O [M+H]+ 189.1279, found 189.1277.
2-(2-溴乙基)-3-甲基-2,3-二氢苯并呋喃(11): 31 mg, 无色油状液体, dr 4∶1, 产率65%. 1H NMR (600 MHz, Chloroform-d) δ: 7.13 (d, J=7.2 Hz, 2H), 6.88 (t, J=7.2 Hz, 1H), 6.78 (d, J=9.0 Hz, 1H), 4.90~4.86 (m, 0.2H), 4.45~4.42 (m, 0.8H), 3.66~3.49 (m, 2H), 3.54~3.49 (m, 0.2H), 3.18~3.13 (m, 0.8H), 2.35~2.26 (m, 1H), 2.24~2.18 (m, 0.8H), 2.12~2.07 (m, 0.2H), 1.36 (d, J=6.6 Hz, 2.4H), 1.21 (d, J=7.2 Hz, 0.6H); 13C NMR (151 MHz, Chloroform-d) δ: 158.7, 158.3, 132.6, 131.8, 128.2, 128.1, 124.0, 123.8, 120.7, 120.6, 109.6, 109.5, 88.2, 83.6, 42.1, 38.8, 38.3, 33.4, 30.2, 29.3, 18.9, 14.9; HRMS (ESI) calcd for C11H14BrO [M+H]+ 241.0028, found 241.0028.
2-(2-氟乙基)-3-甲基-2,3-二氢苯并呋喃(12): 28 mg, 无色油状液体, dr 4∶1, 产率78%. 1H NMR (600 MHz, Chloroform-d) δ: 7.17~7.12 (m, 2H), 6.88 (t, J=7.5 Hz, 1H), 6.78 (d, J=8.4 Hz, 1H), 4.88~4.85 (m, 0.2H), 4.79~4.62 (m, 2H), 4.44~4.40 (m, 0.8H), 3.51~3.47 (m, 0.2H), 3.23~3.18 (m, 1H), 2.21~2.07 (m, 2H), 1.36 (d, J=6.6 Hz, 2.4H), 1.20 (d, J=7.2 Hz, 0.6H); 13C NMR (151 MHz, Chloroform-d) δ: 158.8, 158.4, 132.8, 131.9, 128.1, 124.1, 123.8, 120.6, 120.5, 109.6, 109.5, 86.8 (d, J=4.7 Hz), 81.9 (d, J=5.1 Hz), 81.3 (d, J=164.7 Hz), 80.8 (d, J=164.7 Hz), 42.3, 38.9, 35.8 (d, J=19.5 Hz), 31.0 (d, J=19.6 Hz), 18.7, 15.1; HRMS (ESI) calcd for C11H14FO [M+H]+ 181.1029, found 181.1030.
5-氯-2-环丁基-3-甲基-2,3-二氢苯并呋喃(13): 31 mg, 无色油状液体, dr 19∶1, 产率70%, 1H NMR (400 MHz, Chloroform-d) δ: 7.07~7.03 (m, 2H), 6.68 (d, J=8.2 Hz, 1H), 4.25 (t, J=7.0 Hz, 1H), 3.07~3.0 (m, 1H), 2.64~2.56 (m, 1H), 2.06~1.86 (m, 6H), 1.30 (d, J=7.2 Hz, 3H); 13C NMR (101 MHz, Chloroform-d) δ: 158.0, 134.5, 127.8, 124.7, 124.0, 110.2, 94.2, 40.1, 38.9, 23.8, 23.5, 19.5, 18.2; HRMS (ESI) calcd for C13H16ClO [M+H]+ 223.0890, found 223.0891.
2-环丙基-3-甲基-2,3-二氢苯并呋喃(14): 28.2 mg, 无色油状液体, dr>20∶1产率82%. 1H NMR (400 MHz, Chloroform-d) δ: 7.14~7.10 (m, 2H), 6.88~6.85 (m, 1H), 6.78 (d, J=7.6 Hz, 1H), 3.62 (t, J=8.4 Hz, 1H), 3.40~3.33 (m, 1H), 1.36 (d, J=6.8 Hz, 3H), 1.22~1.14 (m, 1H), 0.70~0.59 (m, 2H), 0.50~0.40 (m, 2H); 13C NMR (101 MHz, Chloroform-d) δ: 159.0, 132.5, 128.0, 123.6, 120.2, 109.3, 95.7, 42.6, 18.9, 14.8, 2.6, 1.3; HRMS (ESI) calcd for C12H15O [M+H]+ 175.1123, found 175.1122.
6-溴-2-环丙基-3-甲基-2,3-二氢苯并呋喃(15): 36.8 mg, 无色油状液体, dr 9∶1, 产率73%. 1H NMR (400 MHz, Chloroform-d) δ: 6.99~6.93 (m, 2H), 6.92~6.91 (m, 1H), 3.97 (t, J=8.8 Hz, 0.11H), 3.65 (t, J=8.2 Hz, 0.9H), 3.44~3.36 (m, 0.1H), 3.32~3.25 (m, 0.9H), 1.33~1.30 (m, 3H), 1.19~1.10 (m, 1H), 0.71~0.58 (m, 2H), 0.51~0.38 (m, 1.9H), 0.32~0.26 (m, 0.1H); 13C NMR (101 MHz, Chloroform-d) δ: 160.0, 159.7, 132.5, 131.8, 125.1, 124.6, 123.3, 123.2, 120.9, 120.8, 112.9, 96.5, 92.7, 42.2, 38.8, 18.9, 15.8, 14.7, 10.4, 3.7, 2.7, 2.0, 1.4; HRMS (ESI) calcd for C12H14BrO [M+H]+ 253.0228, found 253.0224.
5-溴-2-环丙基-3-甲基-2,3-二氢苯并呋喃(16): 34 mg, 无色油状液体, dr 9∶1, 产率67%. 1H NMR (400 MHz, Chloroform-d) δ: 7.23~7.17 (m, 2H), 6.64 (dd, J=8.8, 2.0 Hz, 1H), 3.98~3.94 (m, 0.1H), 3.62 (dd, J=8.4, 2.0 Hz, 0.9H), 3.48~3.42 (m, 0.1H), 3.34 (p, J=7.2 Hz, 0.9H), 1.33 (dd, J=6.8, 2.0 Hz, 3H), 1.20~1.11 (m, 1H), 0.71~0.59 (m, 2H), 0.51~0.38 (m, 1.9H), 0.32~0.27 (m, 0.1H); 13C NMR (101 MHz, Chloroform-d) δ: 158.2, 157.9, 135.7, 135.0, 130.7, 127.1, 126.7, 112.0, 110.9, 110.9, 96.2, 92.4, 42.6, 39.3, 18.8, 15.8, 14.7, 10.4, 3.7, 2.6, 2.0, 1.4; HRMS (ESI) calcd for C12H14BrO [M+H]+ 253.0228, found 253.0229.
5,7-二溴-2-环丙基-3-甲基-2,3-二氢苯并呋喃(17): 36.3 mg, 无色油状液体, dr 1∶1, 产率55%. 1H NMR (600 MHz, Chloroform-d) δ: 7.39 (s, 1H), 7.16 (s, 1H), 4.07 (t, J=9.0 Hz, 1H), 3.53 (q, J=7.8 Hz, 1H), 1.34 (d, J=7.2 Hz, 3H), 1.16~1.10 (m, 1H), 0.76~0.71 (m, 1H), 0.69~0.64 (m, 1H), 0.57~0.53 (m, 1H), 0.32~0.27 (m, 1H); 13C NMR (151 MHz, Chloroform-d) δ: 155.7, 136.4, 133.1, 126.2, 112.1, 103.1, 92.9, 40.4, 15.8, 10.3, 4.1, 2.1; HRMS (ESI) calcd for C12H13Br2O [M+H]+ 330.9333, found 330.9330.
5-氯-2-环丙基-3-甲基-2,3-二氢苯并呋喃(18): 28.7 mg, 无色油状液体, dr 6.9∶1, 产率69%. 1H NMR (400 MHz, Chloroform-d) δ: 7.09~7.04 (m, 2H), 6.70~6.67 (m, 1H), 3.96 (t, J=8.8 Hz, 0.13H), 3.64 (t, J=8.2 Hz, 0.87H), 3.43 (p, J=7.6 Hz, 0.13H), 3.33 (p, J=7.2 Hz, 0.87H), 1.34~1.32 (m, 3H), 1.20~1.11 (m, 1H), 0.72~0.59 (m, 2H), 0.51~0.38 (m, 1.87H), 0.32~0.26 (m, 0.13H); 13C NMR (101 MHz, Chloroform-d) δ: 157.7, 157.4, 135.1, 134.5, 127.8, 124.9, 124.3, 123.8, 110.3, 110.2, 96.3, 92.5, 42.7, 39.3, 18.7, 15.8, 14.7, 10.4, 3.7, 2.6, 2.0, 1.4; HRMS (ESI) calcd for C12H14ClO [M+H]+ 209.0733, found 209.0734.
3-甲基-2-苯基-2,3-二氢苯并呋喃(19): 30 mg, 无色油状液体, dr 1.6∶1, 产率71%. 1H NMR (400 MHz, Chloroform-d) δ: 7.45~7.28 (m, 5H), 7.21~7.14 (m, 2H), 6.95~6.88 (m, 2H), 5.83~5.81 (d, J=8.8 Hz, 0.4H), 5.17 (d, J=8.8 Hz, 0.6H), 3.75~3.67 (m, 0.4H), 3.49~3.42 (m, 0.6H), 1.44 (d, J=6.8 Hz, 2H), 0.82 (d, J=7.2 Hz, 1H); 13C NMR (101 MHz, Chloroform-d) δ: 159.2, 159.1, 140.9, 138.0, 132.7, 131.9, 128.6, 128.2, 128.2, 128.2, 127.6, 126.3, 126.1, 124.4, 123.6, 120.8, 120.8, 109.5, 109.5, 92.4, 87.7, 45.6, 40.9, 18.1, 17.0; HRMS (ESI) calcd for C15H15O [M+H]+ 211.1123, found 211.1125.
2-(2-氟苯基)-3-甲基-2,3-二氢苯并呋喃(20): 30 mg, 无色油状液体, dr>20∶1, 产率66%. 1H NMR (600 MHz, Chloroform-d) δ: 7.47 (td, J=7.8, 1.8 Hz, 1H), 7.31~7.28 (m, 1H), 7.21~7.18 (m, 1H), 7.16~7.13 (m, 2H), 7.10~7.08 (m, 1H), 6.95~6.90 (m, 2H), 5.54 (d, J=7.2 Hz, 1H), 3.47 (p, J=7.2 Hz, 1H), 1.49~1.47 (d, J=7.2 Hz, 3H); 13C NMR (151 MHz, Chloroform-d) δ: 160.1 (d, J=246.6 Hz), 159.0, 131.6, 129.4 (d, J=8.2 Hz), 128.5 (d, J=12.8 Hz), 128.3, 127.3(d, J=4.1 Hz), 124.3 (d, J=3.5 Hz), 123.8, 120.9, 115.4 (d, J=21.3 Hz), 109.5, 85.9 (d, J=2.6 Hz), 45.3, 18.9; HRMS (ESI) calcd for C15H14FO [M+H]+ 229.1029, found 229.1026.
3-(3-甲基-2,3-二氢苯并呋喃-2-基)苯腈(21): 25 mg, 无色油状液体, dr 1.5∶1, 产率53%. 1H NMR (600 MHz, Chloroform-d) δ: 7.73 (s, 0.6H), 7.67~7.65 (m, 1H), 7.63~7.60 (m, 1H), 7.57 (d, J=6.0 Hz, 0.4H), 7.51~7.47 (m, 1H), 7.22~7.14 (m, 2H), 6.97~6.90 (m, 2H), 5.81 (d, J=9.0 Hz, 0.4H), 5.20 (d, J=8.4 Hz, 0.6H), 3.75 (p, J=7.8 Hz, 0.4H), 3.39 (p, J=7.2 Hz, 0.6H), 1.48 (d, J=7.2 Hz, 1.8H), 0.80 (d, J=7.2 Hz, 1.2H); 13C NMR (151 MHz, Chloroform-d) δ: 158.8, 158.6, 142.9, 139.9, 131.9, 131.7, 131.3, 131.00, 130.7, 130.1, 129.9, 129.5, 129.4, 129.1, 128.6, 128.5, 124.4, 123.8, 121.3, 121.3, 118.7, 118.5, 112.8, 112.5, 109.6, 90.7, 86.3, 45.8, 40.7, 18.5, 17.0; HRMS (ESI) calcd for C16H14NO [M+H]+236.1075, found 236.1079.
2-(3,5-二溴苯基)-3-甲基-2,3-二氢苯并呋喃(22): 48.5 mg, 无色油状液体, dr 1.2∶1, 产率66%. 1H NMR (600 MHz, Chloroform-d) δ: 7.62 (dt, J=9.0, 1.8 Hz, 1H), 7.50 (d, J=1.8 Hz, 1H), 7.43 (d, J=1.2 Hz, 1H), 7.21~7.13 (m, 2H), 6.96~6.89 (m, 2H), 5.71 (d, J=9.0 Hz, 0.45H), 5.10 (d, J=7.8 Hz, 0.55H), 3.72~3.67 (m, 0.45H), 3.41~3.36 (m, 0.55H), 1.46 (d, J=6.6 Hz, 1.66H), 0.85 (d, J=7.2 Hz, 1.35H); 13C NMR (151 MHz, Chloroform-d) δ: 158.7, 158.4, 145.2, 142.2, 133.7, 133.3, 132.0, 131.0, 128.5, 128.1, 127.6, 124.4, 123.7, 123.2, 122.9, 121.3, 109.7, 109.6, 90.4, 45.8, 40.8, 18.5, 17.3; HRMS (ESI) calcd for C15H13Br2O [M+H]+366.9333, found 366.9329.
2-(4-氟苯基)-3-甲基-2,3-二氢苯并呋喃(23): 34.3 mg, 无色油状液体, dr 3∶1, 产率75%. 1H NMR (600 MHz, Chloroform-d) δ: 7.40~7.37 (m, 1.5H), 7.28~7.26 (m, 0.5H), 7.18~7.12 (m, 2H), 7.07~7.02 (m, 2H), 6.93~6.85 (m, 2H), 5.77 (d, J=8.4 Hz, 0.25H), 5.12 (d, J=9.0 Hz, 0.75H), 3.66 (p, J=7.8 Hz, 0.25H) 3.39 (p, J=7.2 Hz, 0.75H), 1.41 (d, J=7.2 Hz, 2.25H), 0.80 (d, J=7.2 Hz, 0.75H); 13C NMR (151 MHz, Chloroform-d) δ: 162.6 (d, J=246.4 Hz), 162.3 (d, J=245.8 Hz), 159.0, 158.9, 136.7 (d, J=3.2Hz), 133.8 (d, J=3.2 Hz), 132.5, 131.7, 128.3, 128.2, 128.0 (d, J=8.0 Hz), 127.8 (d, J=8.2 Hz), 124.4, 123.6, 120.9, 115.5 (d, J=21.4 Hz), 115.2 (d, J=21.6 Hz), 109.5, 109.4, 91.71, 87.03, 45.61, 40.82, 18.00, 16.91; 19F NMR (565 MHz, Chloroform-d) δ: -113.95, -114.69; HRMS (ESI) calcd for C15H14FO [M+H]+ 229.1029, found 229.1030.
2-(4-溴苯基)-3-甲基-2,3-二氢苯并呋喃(24): 43.8mg, 无色油状液体, dr 2.1∶1, 产率77%. 1H NMR (600 MHz, Chloroform-d) δ: 7.58 (t, J=1.8 Hz, 1H), 7.49 (t, J=1.8 Hz, 0.7H), 7.46~7.41 (m, 0.3H), 7.33 (dt, J=7.8, 1.5 Hz, 0.7H), 7.25~7.22 (m, 1.3H), 7.20~7.15 (m, 1H), 7.14~7.12 (m, 1H), 6.94~6.90 (m, 1H), 6.88 (d, J=8.0 Hz, 1H), 5.75 (d, J=9.0 Hz, 0.3H), 5.11 (d, J=8.4 Hz, 0.7H), 3.72~3.66 (m, 0.3H), 3.42~3.37 (m, 1H), 1.43 (d, J=6.6 Hz, 2H), 0.81 (d, J=7.2 Hz, 1H); 13C NMR (151 MHz, Chloroform-d) δ: 158.9, 158.7, 143.4, 140.5, 132.3, 131.4, 131.2, 130.7, 130.2, 129.8, 129.3, 129.0, 128.4, 128.3, 125.0, 124.5, 124.4, 123.7, 122.8, 122.5, 121.1, 121.0, 109.5, 91.3, 86.7, 45.7, 40.8, 18.3, 17.1; HRMS (ESI) calcd for C15H14BrO [M+H]+ 289.0228, found 289.0227.