二茂铁骨架n,n配体及其制备方法和应用_2

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, J = 9.0 Hz, 1Η), 4.81 (t, J = 9.2 Hz, 1Η), 4.36 (s, 5Η), 4.34-4.29 (m, 2Η), 4.19 (t, J = 8.3 Hz, 1Η), 0.30 (s, 9Η). 13C 匪R (100 MHz, CDCl3) δ 170.51, 162.83, 148.08, 141.64, 136.45, 130.93, 128.72, 127.69, 126.68, 121.97, 121.30, 96.08, 76.27, 75.56, 74.61, 74.54, 73.41, 70.86, 69.18, 65.58, 30.59, 29.72, 13.76, 0.87; HRMS m/z calcd for C28H30FeN2O2Si [Μ+Η]+ 511.1460, found 511.1500. 化合物3': [α] D25= +289.7。(c=0.5, CH2CI2); m.p. 168.2-169.8 〇C; 1HNMR (400 MHz, CDCl3) δ 8.59 (d, J = 4.6 Hz, 1H), 7.93-7.74 (m, 3H), 7.37-7.24 (m, 5H), 5.84 (s, 1H), 5.47-5.38 (m, 1H), 4.75 (t, J = 9.1 Hz, 1H), 4.34 (s, 5H), 4.26 (t, J = 7.8 Hz, 1H), 4.17-4.12 (m, 2H), 3.77 (d, J=1.8 Hz, 1H), 0.31 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 170.43, 162.26, 148.13, 142.12, 136.65, 128.80, 127.62, 126.28, 122.20, 121.37, 100.62, 75.16, 74.62, 74.42, 74.14, 72.05, 71.17, 70.40, 69.13, 29.72, 21.09, 14.23, 0.69; HRMS m/z calcd for C28H30FeN2O2Si [M+H]+ 511.1460, found 511.1499 〇
[0021 ] 实施实例4:制备(R)-{2-[(S)-4-苄基-4,5-二氢噁唑基]-3-(三甲基硅烷基)苯 基}-(2_吡啶基)-甲醇4和(S)-{2-[(S)-4-苄基-4,5-二氢噁唑基]-3-(三甲基硅烷基)苯 基}_(2_吡啶基)-甲醇4' 制备方法同实施实例1,分别得到目标产物4为红棕色发泡状固体,共1.27g,产率53%; 得到目标产物4'为橘黄色固体,共90Img,产率33%。
[0022]化合物4: [a] D25 = +2 3 0.5。(c=0.36,CH2CI2) ; 1H NMR (400 MHz, CDCl3) δ 8.57 (d, J=4 Hz, 1H), 7.99 (d, J = 5.8 Hz, 1H), 7.78-7.57 (m, 2H), 7.34-7.13 (m, 5H), 5.91 (d, J = 5.6 Hz, 1H), 4.56 (dt, J = 14.9, 8.0 Hz, 1H), 4.40 (t, J = 8.8 Hz, 1H), 4.30 (s, 5H), 4.23 (d, J = 2.1 Hz, 2H), 4.05 (t, J = 8.0 Hz, 1H), 3.12 (dd, J = 13.8, 5.7 Hz, 1H), 2.66 (dd, J = 13.8, 8.1 Hz, 1H), 0.23 (s, 8H). 13C 匪R (100 MHz, CDCl3) δ 169.54, 162.83, 148.40, 137.63, 136.18, 129.13, 128.63, 126.61, 122.00, 121.21, 95.69, 75.92, 75.38, 74.14, 74.10, 73.43, 71.85, 71.71, 70.75, 66.91, 41.52, 0.74; HRMS m/z calcd for C29H32FeN2O2Si [M+H]+ 525.1616, found 525.1653. 化合物4':[a] D25 = +207.4。(c=0.5, CH2CI2); m.p. 105.6~106.9 〇C; 1H 匪R (400 MHz, CDCl3) δ 8.60 (d, J = 4.6 Hz, 1H), 7.92-7.80 (m, 3H), 7.34-7.22 (m, 5H), 5.79 (s, 1H), 4.61-4.54 (m, 1H), 4.33-4.31 (m, 1H), 4.29 (s, 5H), 4.17-4.11 (m, 2H), 4.09 (d, J = 2.0 Hz, 1H), 3.73 (d, J = 2.3 Hz, 1H), 3.13 (dd, J =13.7, 5.4 Hz, 1H), 2.72 (dd, J = 13.7, 8.3 Hz, 1H), 0.26 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 169.47, 162.35, 148.20, 137.69, 136.54, 129.24, 128.57, 126.58, 122.16, 121.34, 100.36, 74.96, 74.41, 73.93, 71.96, 71.37, 70.30, 67.13, 41.84, 0.61; HRMS m/z calcd for C29H32FeN2O2Si [M+H]+ 525.1616, found 525.1660。
[0023] 实施实例5:制备(R)-{2-[(S)_4-异丙基-4,5_二氢噁唑基]苯基}-(2_吡啶基)_甲 醇5和(S)-{2-[(S)-4-异丙基-4,5-二氢噁唑基]苯基}-(2_吡啶基)-甲醇5' 取上述化合物I (953mg, 2.0 mmol)于一50mL干燥史耐克管中,抽真空,充氮气,加入 无水DMSO (5mL),在氮气氛围下,加入叔丁醇钾(538.6mg, 4.8 mmol),于室温下搅拌过 夜,减压浓缩反应液,柱层析纯化得目标产物5为橘黄色固体,共663mg,产率82%。
[0024] [a] D25 = +34 2.1。(c=0.22,CH2CI2); m.p· 80.卜81.2 °C; 1H NMR (400 MHz, CDCl3) δ 8.53 (d, J = 4.7 Hz, 1H), 8.23 (d, J = 6.6 Hz, 1Η), 7.7〇-7.63(m, 2Η), 7.14 (ddd, J = 6.7, 4.9, 1.7 Hz, 1H), 5.84 (d, J = 6.1 Hz, 1H), 4.65 (dd, J = 2.4, 1.6 Hz, 1H), 4.50-4.43 (m, 1H), 4.32 (s, 5Η), 4.27 (dt, J = 4.0, 2.5 Hz, 2Η), 4.08-4.01 (m, 2Η), 1.75 (td, J = 13.2, 6.6 Hz, 1Η), 0.97 (d, J = 6.7 Hz, 3Η), 0.90 (d, J = 6.8 Hz, 3Η). 13C 匪R (100 MHz, CDCl3) δ 168.07, 162.16, 148.05, 136.59, 122.27, 121.49, 95.83, 72.41, 71.96, 70.67, 70.38, 70.19, 69.57, 68.23, 66.44, 33.02, 18.72, 18.57; HRMS m/z calcd for C22H24FeN2O2 [M+H]+ 405.1221, found 405.1263. 化合物5 '由化合物Γ制备而来,制备方法同上。共得452mg,产率67%。
[0025] [a] D25 = +139.1。(c=0.45,CH2CI2); 1H (400 MHz, CDCl3) δ 8.53 (d,J =4.7 Hz, 1H), 8.24 (d, J = 7.9 Hz, 1H), 7.70-7.63 (m, 2H), 7.14 (dd, J = 6.8, 5.0 Hz, 1H), 5.84 (d, J = 7.7 Hz, 1H), 4.65 (dd, J = 2.5, 1.6 Hz, 1H), 4.50-4.43 (m, 1H), 4.32 (s, 5H), 4.28-4.26 (m, 2H), 4.08-4.01 (m, 2H), 1.74 (dt, J = 13.2, 6.6 Hz, 1H), 0.97 (d, J = 6.7 Hz, 3H), 0.90 (d, J = 6.7 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 168.17, 163.26, 148.45, 136.22, 121.91, 120.84, 92.44, 73.67, 72.38, 71.95, 70.76, 70.70, 70.40, 68.78, 66.94, 32.84, 18.76, 18.60; HRMS m/z calcd for C22H24FeN2O2 [M+H]+ 405.1221, found 405.1261〇
[0026] 实施实例6:制备(R)-{2-[(S)_4-叔丁基-4,5_二氢噁唑基]苯基}-(2_吡啶基)_甲 醇6和(S)-{2-[(S)-4-叔丁基-4,5-二氢噁唑基]苯基}-(2_吡啶基)-甲醇6' 制备方法同实施实例5,分别得到目标产物6为橘黄色固体,共763g,产率73%;得到目 标产物6 '为红棕色发泡状固体,共623mg,产率63%。
[0027] 化合物6: [a] D25 = +416.7。(c=0.45, CH2CI2); m.p. 129.5-130.3 °C; 1H NMR (400 MHz, CDCl3) δ 8.58 (d, J = 4.4 Hz, 1H), 8.26 (s, 1H), 7.93 (d, J = 7.8 Hz, 1H), 7.84 (t, J = 7.6 Hz, 1H), 7.26-7.25 (m, 1H), 5.78 (s, 1H), 4.67 (s, 1H), 4.40-4.33 (m, 1H), 4.28 (s, 5H), 4.21-4.15 (m, 2H), 4.05 (dd, J = 9.8, 7.9 Hz, 1H), 3.62 (s, 1H), 0.94 (s, 9H). 13C 匪R (100 MHz, CDCl3) δ 168.08, 162.14, 148.07, 136.60, 122.28, 121.50, 96.05, 75.36, 72.54, 70.45, 70.18, 69.49, 68.80, 68.15, 66.42, 33.70, 25.74; HRMS m/z calcd for C23H26FeN2O2 [M+H ]+ 419.1377, found 419.1416. 化合物6': [a] D25 = +102.3° (c=0.15,CH2CI2); 1H (400 MHz, CDCl3) δ 8.52 (d, J = 4.6 Hz, 1H), 8.25 (s, 1H), 7.70-7.63 (m, 2H), 7.15-7.11 (m, 1H), 5.83 (s, 1H), 4.66 (t, J = 2.0 Hz, 1H), 4.39 (dd, J = 9.7, 8.6 Hz, 1H), 4.32 (s, 5H), 4.28-4.27 (m, 2H), 4.11 (t, J = 8.5 Hz, 1Η), 4.02 (dd, J = 9.7, 8.7 Hz, 1Η), 0.88 (s, 9Η). 13C 匪R (100 MHz, CDCl3) δ 168.17, 163.23, 148.49, 136.20, 121.92, 120.93, 92.43, 75.47, 73.59, 72.47, 70.70, 70.42, 68.94, 68.77, 66.87, 33.65, 25.87; HRMS m/z calcd for C23H26FeN2O2 [M+H]+ 419.1377, found 419·1419。
[0028] 实施实例7:制备(R)-{2-[(S)_4-苯基-4,5-二氢噁唑基]苯基}-(2_吡啶基)_甲醇 7和(S)-{2-[(S)-4-苯基-4,5-二氢噁唑基]苯基}-(2_吡啶基)-甲醇7' 制备方法同实施实例5,分别得到目标产物7为红棕色发泡状固体,共663g,产率63%; 得到目标产物7'为红棕色发泡状固体,共513mg,产率76%。
[0029] 化合物7: [a] D25 = +401.9。(c=0.42,CH2CI2); 1H (400 MHz, CDCl3) δ 8.59 (t, J = 4.9 Hz, 1H), 7.87-7.84 (m, 1H), 7.78 (td, J = 7.7, 1.6 Hz, 1H), 7.63 (s, 1H), 7.46-7.39 (m, 3H), 7.38-7.35 (m, 1Η), 7.31-7.29 (m, 1Η), 7.26- 7.23 (m, 1Η), 5.90 (d, J = 11.3 Hz,
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