CN115232066B - 一种光催化烯烃合成1,2-烷基芳基乙烷化合物的方法 - Google Patents

一种光催化烯烃合成1,2-烷基芳基乙烷化合物的方法 Download PDF

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CN115232066B
CN115232066B CN202210815455.3A CN202210815455A CN115232066B CN 115232066 B CN115232066 B CN 115232066B CN 202210815455 A CN202210815455 A CN 202210815455A CN 115232066 B CN115232066 B CN 115232066B
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王涛
余维洁
蓝金平
江周
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Abstract

本发明一种光催化烯烃合成1,2‑烷基芳基乙烷化合物的方法是在可见光的作用下，借助铱光催化剂，烯烃、对氰基吡啶和烷基碘代烃以自由基串联反应的形式，合成1,2‑烷基芳基乙烷化合物。本发明采用可见光氧化还原方法，避免了添加过渡金属催化剂、高反应活性的有机金属试剂、金属还原试剂以及螯合导向基团的协助。可见光催化条件温和，反应操作简单，反应可控，最为重要的是这一方法精确控制区域和化学选择性获得具有潜在生理学活性的1,2‑烷基芳基乙烷化合物，更好地实现其潜在应用价值。

Description

一种光催化烯烃合成1,2-烷基芳基乙烷化合物的方法
技术领域
本发明涉及一种光催化烯烃合成1,2-烷基芳基乙烷化合物的方法，具体属于有机化学和生物化学领域。
背景技术
烯烃是化工生产中基础的大宗化学品，引入两个的原子和基团(包括碳原子和杂原子)到烯烃C＝C的两端，不但可以迅速增加产物分子的多样性，而且能够减少合成步骤，所以这一研究领域近年来得到了迅猛发展，成为当前有机化学研究的热点和前沿。其中，1,2-烷基芳基乙烷是一类非常重要的化合物，广泛存在于有机功能材料、药物及活性分子中，如下面结构式所示。
经典的过渡金属催化合成1,2-烷基芳基乙烷的方法，通常是过渡金属与亲电体发生氧化加成，随后发生烯烃的迁移插入，再与一分子的金属亲核试剂发生转金属化，还原消除得到烷基芳基化产物。该方法需要高反应活性的有机锌，有机格式试剂等参与反应，或者需要螯合导向基团协助，极大限制了该反应的进一步转化应用。近年来，可见光参与的自由基加成反应是实现烯烃双官能团化的重要手段。这类反应由于反应条件温和，具有很好的区域选择性，是当前有机化学的研究热点。Chu，Nevado，Molander，Aggawal，Yuan，Kong等课题组发展了各种亲核试剂前体作为烷基自由基源，可见光促进的可见光/镍协同催化模式得到1,2-烷基芳基乙烷化合物，该方法最大的不足在于需要使用空气敏感的金属镍催化剂(如Ni(cod)2)以及配体，极大增加了进一步的工业化成本，另外，对于底物限制性较大，通常选用位阻较大的叔碳自由基作为烷基自由基源参与反应来避免两组分交叉偶联，难以满足多样性分子设计需求。因此，开发出一种新颖的无导向基团协助，无金属镍催化剂，不添加任何配体的烯烃1,2-烷基芳基化策略，解决底物适用性的局限，实现烯烃的高区域选择性控制，合成具有高附加值1,2-烷基芳基乙烷类化合物，是一个当下仍需解决的问题。
发明内容
本发明目的在于开发了一种可见光氧化还原催化模式新型方案，提供了一种简洁、模块化可见光催化方法高区域选择性精准合成1,2-烷基芳基乙烷。
本发明一种光催化烯烃合成1,2-烷基芳基乙烷化合物的方法是在可见光的作用下，借助铱光催化剂(Ir[dFCF3(ppy)2(dtbbpy)PF6])，烯烃、对氰基吡啶和烷基碘代烃以自由基串联反应的形式，合成1,2-烷基芳基乙烷化合物；
具体步骤为：在装有搅拌子反应管中加入铱光催化剂和对氰基吡啶，氮气抽排3次后，将烯烃、烷基碘代烃、胺加入反应管中，并在460nm蓝光照射下反应24h；产物经后处理得到1,2-烷基芳基乙烷化合物；所述的铱光催化剂的用量为烯烃的摩尔百分比是1％。
所述的对氰基吡啶、烯烃、烷基碘代烃和胺的摩尔比为：当烷基碘代烃是一级烷基碘代烃时为1.5∶1∶5∶5；当烷基碘代烃是二级或三级烷基碘代烃时为1.5∶1∶1.5∶3。
所述的胺为N,N,N,N-四甲基乙二胺、三乙胺、N,N-二甲基乙酰胺和2-甲基四氢呋喃中的一种或两种。
所述的后处理为：2-甲基四氢呋喃作溶剂时，产物的有机层经浓缩、柱层析处理；N,N-二甲基乙酰胺作溶剂时，产物经水洗、乙酸乙酯萃取、有机相浓缩和柱层析。
本发明机理如下：
光催化剂IrⅢ在蓝光照射条件下得到激发态*IrⅢ，优先与有机胺试剂发生单电子转移，得到α-氨基烷基自由基，与烷基碘代烃发生卤原子转移，得到新的烷基自由基，加成到烯烃得到苄基自由基Ⅰ，还原态的光催化剂IrⅡ与氰基吡啶发生单电子转移得到中间体Ⅱ，并完成光催化循环，苄基自由基与氰基吡啶自由基阴离子中间体发生自由基耦合，得到中间体，脱氰基芳构化得到最终的1,2-烷基芳基化合物。
反应通式如下：
其中：式中Ar代表各种富电子、缺电子取代的芳基，Het代表吡啶等杂芳环，R代表一级、二级、三级烷基取代基。
本发明的有益效果：本发明采用可见光氧化还原方法，避免了添加过渡金属催化剂、高反应活性的有机金属试剂、金属还原试剂以及螯合导向基团的协助。可见光催化条件温和，反应操作简单，反应可控，最为重要的是这一方法精确控制区域和化学选择性获得具有潜在生理学活性的1,2-烷基芳基乙烷化合物，更好地实现其潜在应用价值。
具体实施方式
实施例1
合成
(1)在干净，装有搅拌子的25mL规格反应管中加入对氰基吡啶(0.3mmol,31.2mg)，Ir[dFCF3(ppy)2(dtbbpy)PF6](0.002mmol,2.2mg),反应管氮气抽排3次，将4-甲基苯乙烯(0.2mmol,23.6mg)，3,7-二甲基-1-碘辛烷(1.0mmol,268.0mg)，三乙胺(1.0mmol,101.2mg)溶于3.0mL 2-甲基四氢呋喃溶剂中缓慢加入，在460nm蓝光照射下反应24h，TLC点板监测。
(2)反应结束后，反应液浓缩并经过柱层析得到纯的上述1,2-烷基芳基乙烷化合物，收率60％。
1H NMR(400MHz,CDCl3)δ8.47(d,J＝4.4Hz,2H),7.21–7.04(m,6H),3.83(t,J＝8.0Hz,1H),2.31(s,3H),2.06–1.88(m,3H),1.56–1.42(m,1H),1.37–1.16(m,7H),1.14–1.07(m,3H),0.85(d,J＝6.4Hz,6H),0.78(d,J＝6.4Hz,3H).
13C NMR(100MHz,CDCl3)δ154.7,154.7,149.9,140.5,140.5,136.3,129.5,127.9,127.8,123.4,50.5,39.5,37.4,37.3,37.0,35.5,32.7,28.1,25.4,24.9,22.8,22.7,21.1,19.8,19.8.
HRMS(ESI+):calcd.For C24H36N(M+H+):388.2842,found:388.2841.
实施例2
合成
(1)在干净，装有搅拌子的25mL规格反应管中加入对氰基吡啶(0.3mmol,31.2mg)，Ir[dFCF3(ppy)2(dtbbpy)PF6](0.002mmol,2.2mg),反应管氮气抽排3次，将4-甲基苯乙烯(0.2mmol,23.6mg)，1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-十七氟-10-碘庚烷(1.0mmol,474mg),三乙胺(1.0mmol,101.2mg)溶于3.0mL 2-甲基四氢呋喃溶剂中缓慢加入，在460nm蓝光照射下反应24h，TLC点板监测。
(2)反应结束后，反应液浓缩并经过柱层析得到纯的上述1,2-烷基芳基乙烷化合物，收率27％。
1H NMR(400MHz,CDCl3)δ8.49(d,J＝4.8Hz,2H),7.19–7.05(m,6H),3.85(t,J＝8.0Hz,1H),2.31(s,3H),2.17–2.03(m,4H),1.64–1.53(m,2H).
13C NMR(100MHz,CDCl3)δ153.7,150.1,139.4,136.8,129.7,127.7,123.1,50.4,34.5,30.8(t,J＝22.5Hz),21.1,18.9(t,J＝3.2Hz).
19F NMR(376MHz,CDCl3)δ-80.84(t,J＝10.8Hz),-114.23(dt,J＝35.1,17.4Hz),-119.56–-121.96(m),-122.87(s),-123.57(d,J＝15.2Hz),-125.18–-127.73(m).
HRMS(ESI+):calcd.For C22H19F13N(M+H+):544.1304,found:544.1286.
实施例3
合成
(1)在干净，装有搅拌子的25mL规格反应管中加入对氰基吡啶(0.3mmol,31.2mg)，Ir[dFCF3(ppy)2(dtbbpy)PF6](0.002mmol,2.2mg),反应管氮气抽排3次，将4-甲基苯乙烯(0.2mmol,23.6mg)，3-碘氧杂环丁烷(0.3mmol 55.2mg)，N,N,N,N-四甲基乙二胺(0.6mmol,69.6mg)溶于3.0mLN,N-二甲基乙酰胺溶剂中缓慢加入，在460nm蓝光照射下反应24h，TLC点板监测。
2)反应结束后，反应液加入10mL蒸馏水，乙酸乙酯萃取3-4次，合并有机相浓缩并经过柱层析得到纯的上述1,2-烷基芳基乙烷化合物，淡黄色液体，收率95％。
1H NMR(400MHz,CDCl3)δ8.49(d,J＝5.6Hz,2H),7.16–7.08(m,4H),7.05(d,J＝8.0Hz,2H),4.66(dd,J＝7.6,6.0Hz,1H),4.59(dd,J＝7.6,6.0Hz,1H),4.36(t,J＝6.0Hz,1H),4.27(t,J＝6.0Hz,1H),3.72(t,J＝7.6Hz,1H),2.99–2.85(m,1H),2.42(t,J＝7.6Hz,2H),2.31(s,3H).
13C NMR(100MHz,CDCl3)δ153.5,150.0,139.2,136.8,129.6,127.7,123.1,77.3,77.3,48.4,38.9,33.8,21.1.
HRMS(ESI+):calcd.For C17H20NO(M+H+):254.1539,found:254.1541.
实施例4
合成
(1)在干净，装有搅拌子的25mL规格反应管中加入对氰基吡啶(0.3mmol,31.2mg)，Ir[dFCF3(ppy)2(dtbbpy)PF6](0.002mmol,2.2mg),反应管氮气抽排3次，将4-甲基苯乙烯(0.2mmol,23.6mg)，1-碘代环十二烷(0.3mmol,88.2mg)，N,N,N,N-四甲基乙二胺(0.6mmol,69.6mg)溶于3.0mLN,N-二甲基乙酰胺溶剂中缓慢加入，在460nm蓝光照射下反应24h，TLC点板监测。
2)反应结束后，反应液加入10mL蒸馏水，乙酸乙酯萃取3-4次，合并有机相浓缩并经过柱层析得到纯的上述1,2-烷基芳基乙烷化合物，淡黄色液体，收率72％。
1H NMR(400MHz,CDCl3)δ8.46(d,J＝4.4Hz,2H),7.20–7.06(m,6H),3.96(t,J＝8.0Hz,1H),2.30(s,3H),1.94–1.86(m,2H),1.39–1.12(m,23H).
13C NMR(100MHz,CDCl3)δ154.7,149.9,140.5,136.3,129.4,127.9,123.4,47.9,40.5,31.4,29.3,29.0,24.8,24.1,23.4,23.2,21.6,21.5,21.1.
HRMS(ESI+):calcd.For C26H38N(M+H+):364.2999,found:364.2992.
实施例5
合成
(1)在干净，装有搅拌子的25mL规格反应管中加入对氰基吡啶(0.3mmol,31.2mg)，Ir[dFCF3(ppy)2(dtbbpy)PF6](0.002mmol,2.2mg),反应管氮气抽排3次，将4-甲基苯乙烯(0.2mmol,23.6mg)，3-碘-1-噻吩-2-甲酸丁酯(0.3mmol,92.7mg)，N,N,N,N-四甲基乙二胺(0.6mmol,69.6mg)溶于3.0mLN,N-二甲基乙酰胺溶剂中缓慢加入，在460nm蓝光照射下反应24h，TLC点板监测。
2)反应结束后，反应液加入10mL蒸馏水，乙酸乙酯萃取3-4次，合并有机相浓缩并经过柱层析得到纯的上述1,2-烷基芳基乙烷化合物，淡黄色液体，收率70％。
1H NMR(400MHz,CDCl3)δ8.43(d,J＝5.6Hz,2H),7.68(d,J＝2.8Hz,1H),7.52(d,J＝4.4Hz,1H),7.14(t,J＝5.2Hz,2H),7.12–7.02(m,5H),4.40–4.30(m,1H),4.29–4.22(m,1H),4.04–3.95(m,1H),2.27(d,J＝4.0Hz,3H),2.18–2.08(m,1H),1.91–1.77(m,2H),1.66–1.49(m,2H),1.04–0.94(m,3H).
13C NMR(100MHz,CDCl3)δ162.2,154.5,153.8,149.9,149.9,140.3139.4,136.4,136.3,134.0,133.9,133.3,133.3,132.4,132.3,129.5,129.4,127.9,127.8,127.7,127.7,123.3,123.1,63.1,63.0,47.7,42.2,42.1,35.8,35.4,27.4,21.0,19.7,19.5.
HRMS(ESI+):calcd.For C23H26NO2S(M+H+):380.1679,found:380.1679.
实施例6
合成
(1)在干净，装有搅拌子的25mL规格反应管中加入对氰基吡啶(0.3mmol,31.2mg)，Ir[dFCF3(ppy)2(dtbbpy)PF6](0.002mmol,2.2mg),反应管氮气抽排3次，将4-甲基苯乙烯(0.2mmol,23.6mg)，3,7-二氢-3,7-二甲基-1-(5-碘)-1H-嘌呤-2,6-二酮(0.3mmol,117.0mg),N,N,N,N-四甲基乙二胺(0.6mmol,69.6mg)溶于3.0mLN,N-二甲基乙酰胺溶剂中缓慢加入，在460nm蓝光照射下反应24h，TLC点板监测。
2)反应结束后，反应液加入10mL蒸馏水，乙酸乙酯萃取3-4次，合并有机相浓缩并经过柱层析得到纯的上述1,2-烷基芳基乙烷化合物，淡黄色液体，收率70％。
1H NMR(400MHz,CDCl3)δ8.45(t,J＝6.0Hz,2H),7.50(s,1H),7.15(t,J＝6.0Hz,2H),7.10(d,J＝3.2Hz,4H),3.97(t,J＝6.4Hz,6H),3.57(s,3H),2.30(d,J＝3.2Hz,3H),2.12–2.02(m,1H),1.80–1.69(m,1H),1.64–1.54(m,2H),1.45–1.35(m,2H),1.32–1.19(m,3H),0.91(t,J＝6.4Hz,3H).
13C NMR(100MHz,CDCl3)δ155.4,155.0,154.3,151.6,149.9,149.8,148.9,141.5,140.8,139.9,136.3,136.3,129.5,129.4,128.0,127.7,123.4,123.2,107.8,47.9,47.8,42.5,42.5,41.4,36.9,36.6,33.6,30.3,30.3,29.8,28.4,28.3,24.3,24.2,21.1,21.0,19.7,19.5.
HRMS(ESI+):calcd.For C27H34N5O2(M+H+):460.2707,found:460.2698.
实施例7
合成
(1)在干净，装有搅拌子的25mL规格反应管中加入对氰基吡啶(0.3mmol,31.2mg)，Ir[dFCF3(ppy)2(dtbbpy)PF6](0.002mmol,2.2mg),反应管氮气抽排3次，将4-甲基苯乙烯(0.2mmol,23.6mg)，1-碘代金刚烷(0.3mmol,78.6mg)，N,N,N,N-四甲基乙二胺(0.6mmol,69.6mg)溶于3.0mL 2-甲基四氢呋喃溶剂中缓慢加入，在460nm蓝光照射下反应24h，TLC点板监测。
2)反应结束后，反应液浓缩并经过柱层析得到纯的上述1,2-烷基芳基乙烷化合物，白色固体，熔点：98-100℃，收率56％。
1H NMR(400MHz,CDCl3)δ8.44(d,J＝5.6Hz,2H),7.18(d,J＝5.6Hz,2H),7.14(d,J＝8.0Hz,2H),7.07(d,J＝7.6Hz,2H),4.05(t,J＝6.4Hz,1H),2.28(s,3H),1.95–1.90(m,2H),1.87(s,3H),1.64(d,J＝12.0Hz,3H),1.55(d,J＝12.0Hz,3H),1.41(s,6H).
13C NMR(100MHz,CDCl3)δ156.2,149.8,142.2,136.0,129.4,127.7,123.2,49.9,45.5,43.2,37.0,33.6,28.7,21.0.
HRMS(ESI+):calcd.For C24H30N(M+H+):332.2373,found:332.2375.
实施例8
合成
(1)在干净，装有搅拌子的25mL规格反应管中加入对氰基吡啶(0.3mmol,31.2mg)，Ir[dFCF3(ppy)2(dtbbpy)PF6](0.002mmol,2.2mg),反应管氮气抽排3次，将4-甲基苯乙烯(0.2mmol,23.6mg)，1-甲基1-碘环己烷(0.3mmol,67.2mg)，N,N,N,N-四甲基乙二胺(0.6mmol,69.6mg)溶于3.0mL 2-甲基四氢呋喃溶剂中缓慢加入，在460nm蓝光照射下反应24h，TLC点板监测。
2)反应结束后，反应液浓缩并经过柱层析得到纯的上述1,2-烷基芳基乙烷化合物，淡黄色液体，收率62％。
1H NMR(400MHz,CDCl3)δ8.44(d,J＝6.0Hz,2H),7.20(d,J＝6.0Hz,2H),7.15(d,J＝8.0Hz,2H),7.07(d,J＝8.0Hz,2H),4.01(t,J＝6.5Hz,1H),2.28(s,3H),2.10(dd,J＝14.0,6.4Hz,1H),2.05(dd,J＝14.4,6.4Hz,1H),1.44–1.32(m,5H),1.26–1.16(m,5H),0.78(s,3H).
13C NMR(100MHz,CDCl3)δ156.3,149.8,142.2,136.1,129.4,127.7,123.3,47.8,46.6,38.6,38.5,34.1,26.4,25.3,22.1,22.1,21.0.
HRMS(ESI+):calcd.For C21H28N(M+H+):294.2216,found:294.2217。

Claims (3)

1.一种光催化烯烃合成1,2-烷基芳基乙烷化合物的方法，其特征在于：所述的方法是在可见光的作用下，借助铱光催化剂，烯烃、对氰基吡啶和烷基碘代烃以自由基串联反应的形式，合成1,2-烷基芳基乙烷化合物；
具体步骤为：在装有搅拌子反应管中加入铱光催化剂和对氰基吡啶，氮气抽排3次后，将烯烃、烷基碘代烃、胺加入反应管中，并在460 nm蓝光照射下反应24 h；产物经后处理得到1,2-烷基芳基乙烷化合物；所述的铱光催化剂的用量为烯烃的摩尔百分比是1%；
所述的胺为N,N,N,N-四甲基乙二胺或三乙胺。
2.根据权利要求1所述的一种光催化烯烃合成1,2-烷基芳基乙烷化合物的方法，其特征在于：所述的对氰基吡啶、烯烃、烷基碘代烃和胺的摩尔比为：当烷基碘代烃是一级烷基碘代烃时为1.5∶1∶5∶5；当烷基碘代烃是二级或三级烷基碘代烃时为1.5∶1∶1.5∶3。
3.根据权利要求1所述的一种光催化烯烃合成1,2-烷基芳基乙烷化合物的方法，其特征在于：所述的后处理为：2-甲基四氢呋喃作溶剂时，产物的有机层经浓缩、柱层析处理；N, N-二甲基乙酰胺作溶剂时，产物经水洗、乙酸乙酯萃取、有机相浓缩和柱层析。
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