CN115417782A - 一种“链行走”式烯烃转移氢化或氢氘化还原方法 - Google Patents

一种“链行走”式烯烃转移氢化或氢氘化还原方法 Download PDF

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CN115417782A
CN115417782A CN202210467121.1A CN202210467121A CN115417782A CN 115417782 A CN115417782 A CN 115417782A CN 202210467121 A CN202210467121 A CN 202210467121A CN 115417782 A CN115417782 A CN 115417782A
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宋恒
周虎
沈洋
丁丹丽
马腾
蔡星伟
徐晨
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Jiangsu University of Science and Technology
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Abstract

本发明公开了一种“链行走”式烯烃转移氢化或氢氘化的还原方法，一步进行，将烯烃衍生物、还原剂、溶剂、水或重水和镍盐加入到反应器中，加热，反应通过TLC薄层色谱检测反应是否完全，待反应结束后，通过柱层析即得烯烃转移氢化或氘化的产物。与现有技术相比，本发明具有以下优点：(1)本发明所述方法以以重水(或水)作为质子源，在还原剂和催化剂存在条件下一步获得烯烃的转移氢氘化(或氢化)产物，氘元素在特定位置，提供了一种更加绿色、经济的方法；(2)所述反应是在接近室温的条件下进行，因此反应条件温和、方法操作简单、产率高、经济高效，具有重要的应用价值和应用前景。

Description

一种“链行走”式烯烃转移氢化或氢氘化还原方法
技术领域
本发明属于有机合成领域，具体涉及烯烃转移氢化、氢氘化还原的反应，该方法简单易操作，反应条件温和，且利用水(或重水)为质子源。
背景技术
有机分子的区域选择性同位素标记可用于有机、金属有机和生物化学，因为同位素标记化合物可用于阐明反应机理和生物合成途径。动力学同位素效应可以测量氘-碳键断裂是否为反应的决速步。目前报道的由过渡金属催化、非金属催化烯烃氢氘化还原反应，氘元素通常只存在于烯烃双键所在的位置，其他位置不含或很少含氘，并且大多利用醇或胺作为质子源。相较于，我们以水或重水作为质子源，在温和的反应条件下一步获得烯烃的转移氢氘化(或氢化)产物，与传统转移氢氘化方法所合成产物中氘元素在双键一侧不同，本发明所合成的含氘产物，氘元素在非双键位置。而使用传统方法难以合成这种产物，该方法为合成特定位置含氘化学品提供了全新的方法，且操作简单、产率高、经济效率高，有很好的应用前景。
发明内容
本发明的目的是提供一种全新的方法对烯烃进行转移氢化、氘化还原，该方法用水作为质子源(或重水作为氘源)，符合绿色可持续发展的要求。另一方面，本发明所使用的反应条件温和，有很好的工业生产前景。
基于上述目的，本发明采用了如下技术方案：取烯烃衍生物、还原剂、溶剂、水或重水和镍配合物加入到反应器中，加热，反应通过TLC薄层色谱检测反应是否完全，待反应结束后，通过柱层析即得烯烃转移氢化或氘化还原的产物。
反应式如下：
Figure BDA0003624827360000021
其中：烯烃衍生物原料碳碳双键均在端位，R1和R2可以是-H、-Me、-Ph、-Bn、-Bu、-tBu、-nBu、-2-SCH3-Ph、-3-I-Ph、-3-NO2-Ph、-4-F-Ph、-4-Cl-Ph、-4-Br-Ph、-4-MeO-Ph等。烯烃转移氢氘化还原产物，通式为：
Figure BDA0003624827360000022
具体获得的产物可以是：
迁移氢氘化产物
Figure BDA0003624827360000031
烯烃转移氢化还原产物，通式为：
Figure BDA0003624827360000032
具体结构可以是：
迁移氢化产物
Figure BDA0003624827360000041
作为进一步的改进，其特征是，所用的还原剂为频哪醇硼烷或三乙氧基硅烷。
作为进一步的改进，其特征是，所用的镍源为溴化镍、碘化镍、氯化镍。
作为进一步的改进，其特征是，所用的配体为2,2'-联吡啶、6,6'-二甲基-2,2'-联吡啶、4,4'-二叔丁基-2,2'-联吡啶。
作为进一步的改进，其特征是，所用的溶剂为二氯甲烷、四氢呋喃。
作为进一步的改进，其特征是，所述的烯烃衍生物、还原剂、镍源、配体、水(或重水)的摩尔比为1：3～6.0：0.02～0.10：0.024～0.12：2～4.0。
作为进一步的改进，其特征是，所述的反应温度为20℃～50℃，反应时间10-24小时，反应结束后用柱层析对产物进行提纯。
本发明的有益效果：本发明的方法中利用商品可得重水(或蒸馏水)作为氘源(或氢源)，配合常规的镍催化剂和配体，可以一步生成烯烃转移氢氘化或氢化的还原产物，提供了一个操作简单、产率高、经济高效的方法，整个反应过程的温度在接近室温条件下进行，反应条件温和，具有重要的应用价值。
说明书附图
图1-3是氘化还原产物中2a的核磁共振图(包括1H，2H和13C NMR)；
图4-7是氘化还原产物中2b的核磁共振图(包括1H，2H和13C NMR)；
图8-10是氘化还原产物中2c的核磁共振图(包括1H，2H和13C NMR)；
图11-13是氘化还原产物中2d的核磁共振图(包括1H，2H和13C NMR)；
图14-16是氢化还原产物2e的核磁共振图(包括1H和13C NMR)；
图17-19是氢化还原产物2f的核磁共振图(包括1H和13C NMR)；
图20-22是氢化还原产物2g的核磁共振图(包括1H和13C NMR)；
图23-25是氢化还原产物2r的核磁共振图(包括1H和13C NMR)。
具体实施方式
为了加深对本发明的理解，下面将结合实施例对本发明做进一步详细描述，该实施例仅用于解释本发明，并不对保护范围构成限定。
参考上述的烯烃转移氢氘化还原产物和烯烃转移氢化还原产物的具体结构，选取对应的产物进行实施例。
实施例1
烯烃转移氢氘化还原产物(2a)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol N-苯基戊-4-烯酰胺、0.01mmol溴化镍、0.012mmol 2,2'-联吡啶、1mL二氯甲烷、0.6mmol HBpin、0.4mmol重水，然后在双排管中通入氮气磁力搅拌下用油浴加热至20℃，反应10小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:20,v:v)为洗脱剂，柱层析后得纯产品，产率99％。该产品的质谱分析数据如下：理论值，179.1295；实验值，179.1299。1H NMR(400MHz,Chloroform-d)δ7.51(d,J＝7.5Hz,2H),7.39(s,1H),7.32–7.26(m,2H),7.08(t,J＝7.4Hz,1H),2.36–2.32(m,1.03H),1.72–1.65(m,2H),1.39(dt,J＝15.0,7.4Hz,2H),0.92(t,J＝7.3Hz,3H).13C NMR(101MHz,Chloroform-d)δ171.78,138.12,129.05,124.25,119.96,37.62,27.82,22.49,13.93.2H NMR(61MHz)δ7.25,2.35。
实施例2
烯烃转移氢氘化还原产物(2b)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol N-(4-溴苯基)戊-4-烯酰胺、0.012mmol氯化镍、0.015mmol 6,6'-二甲基-2,2'-联吡啶、1mL四氢呋喃、0.8mmol HBpin、0.6mmol重水，然后在双排管中通入氮气磁力搅拌下用油浴加热至30℃，反应15小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:20,v:v)为洗脱剂，柱层析后得纯产品，产率85％。该产品的质谱分析数据如下：理论值，257.0400；实验值，257.0411。1H NMR(400MHz,Chloroform-d)δ7.40(s,4H),7.38(t,J＝1.9Hz,1H),2.35–2.31(m,1.10H),1.71–1.64(m,2H),1.38(dt,J＝15.1,7.4Hz,2H),0.92(t,J＝7.4Hz,3H).13C NMR(101MHz,Chloroform-d)δ171.72,137.12,132.01,121.46,116.79,37.59,27.70,22.48,13.94.2H NMR(61MHz,)δ7.26,2.33。
实施例3
烯烃转移氢氘化还原产物(2c)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol N-(4-甲氧基苯基)戊-4-烯酰胺、0.014mmol氯化镍、0.017mmol 6,6'-二甲基-2,2'-联吡啶、1mL四氢呋喃、1.0mmol HBpin、0.6mmol重水，然后在双排管中通入氮气磁力搅拌下用油浴加热至30℃，反应24小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:10,v:v)为洗脱剂，柱层析后得纯产品，产率84％。该产品的质谱分析数据如下：理论值，209.1400；实验值，209.1423。1H NMR(400MHz,Chloroform-d)δ7.42–7.36(m,2H),7.28(s,1H),6.82(d,J＝9.0Hz,2H),3.76(s,3H),2.33–2.29(m,1.12H),1.68(qd,J＝7.5,6.1Hz,2H),1.39(dq,J＝9.3,7.4,7.0Hz,2H),0.92(t,J＝7.3Hz,3H).13CNMR(101MHz,Chloroform-d)δ171.51,156.38,131.18,121.87,114.17,55.56,37.44,27.88,22.48,13.94.2H NMR(61MHz,)δ7.25,2.31。
实施例4
烯烃转移氢氘化还原产物(3d)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol N-(3,5-二氟苯基)戊-4-烯酰胺、0.02mmol溴化镍、0.024mmol 4,4'-二叔丁基-2,2'-联吡啶、1mL四氢呋喃、1.2mmol HBpin、0.8mmol重水，然后在双排管中通入氮气磁力搅拌下用油浴加热至50℃，反应12小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:20,v:v)为洗脱剂，柱层析后得纯产品，产率95％。该产品的质谱分析数据如下：理论值，215.1106；实验值，215.1114。1H NMR(400MHz,Chloroform-d)δ7.73(s,1H),7.16–7.09(m,2H),6.52(tt,J＝9.0,2.3Hz,1H),2.37–2.33(m,1.11H),1.71–1.62(m,2H),1.40–1.32(m,2H),0.91(t,J＝7.4Hz,3H).13C NMR(101MHz,Chloroform-d)δ172.14,164.52,164.38,162.08,161.93,140.20,102.97,102.88,102.68,99.70,99.45,99.19,37.57,27.54,22.40,22.38,13.84.19F NMR(376MHz,Chloroform-d)δ-108.84.2HNMR(61MHz)δ7.24,2.37。
实施例5
烯烃转移氢氘化还原产物(3e)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol N-(2-(甲硫基)苯基)戊-4-烯酰胺、0.01mmol碘化镍、0.012mmol 6,6'-二甲基-2,2'-联吡啶、1mL二氯甲烷、0.8mmol HBpin、0.4mmol重水，然后在双排管中通入氮气磁力搅拌下用油浴加热至30℃，反应15小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:30,v:v)为洗脱剂，柱层析后得纯产品，产率89％。该产品的质谱分析数据如下：理论值，225.1172；实验值，225.1180。1H NMR(400MHz,Chloroform-d)δ8.32(d,J＝8.2Hz,1H),8.30(s,1H),7.46(d,J＝7.8Hz,1H),7.32–7.25(m,1H),7.05(t,J＝7.6Hz,1H),2.42(t,J＝7.6Hz,1.09H),2.36(s,3H),1.73(p,J＝8.3,7.9Hz,2H),1.42(h,J＝7.4Hz,2H),0.95(t,J＝7.3Hz,3H).13C NMR(101MHz,Chloroform-d)δ171.59,138.48,133.02,129.04,125.06,124.32,120.66,37.94,27.79,22.46,19.04,13.93.2H NMR(61MHz,)δ7.25,2.43。
实施例6
烯烃转移氢氘化还原产物(3f)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol N-甲基-N-苯基戊-4-烯酰胺、0.012mmol碘化镍、0.015mmol 6,6'-二甲基-2,2'-联吡啶、1mL四氢呋喃、0.6mmol HBpin、0.4mmol重水，然后在双排管中通入氮气磁力搅拌下用油浴加热至30℃，反应9小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:10,v:v)为洗脱剂，柱层析后得纯产品，产率82％。该产品的质谱分析数据如下：理论值，193.1451；实验值，193.1455。1H NMR(400MHz,Chloroform-d)δ7.40(t,J＝7.5Hz,2H),7.32(t,J＝7.4Hz,1H),7.18–7.14(m,2H),3.24(s,3H),2.07–2.01(m,1.05H),1.52(q,J＝7.9Hz,2H),1.18(h,J＝7.1Hz,2H),0.78(t,J＝7.3Hz,3H).13C NMR(101MHz,Chloroform-d)δ173.48,144.35,129.82,127.80,127.44,37.41,33.89,27.79,22.49,13.92.2H NMR(61MHz,)δ7.24,2.06。
实施例7
烯烃转移氢氘化还原产物(2g)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol N-(叔丁基)戊-4-烯酰胺、0.01mmol溴化镍、0.012mmol6,6'-二甲基-2,2'-联吡啶、1mL二氯甲烷、0.8mmol HBpin、0.4mmol重水，然后在双排管中通入氮气磁力搅拌下用油浴加热至32℃，反应15小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:40,v:v)为洗脱剂，柱层析后得纯产品，产率91％。该产品的质谱分析数据如下：理论值，159.1608；实验值，159.1611。1H NMR(400MHz,Chloroform-d)δ5.26(s,1H),2.06(d,J＝7.8Hz,1H),1.57(dt,J＝14.8,7.4Hz,2H),1.33(d,J＝1.1Hz,11H),0.90(t,J＝7.4Hz,3H).13C NMR(101MHz,Chloroform-d)δ172.64,51.11,37.57,28.92,27.97,22.43,13.96.2H NMR(61MHz,)δ7.26,2.06。
实施例8
烯烃转移氢氘化还原产物(2h)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol N-苄基戊-4-烯酰胺、0.012mmol溴化镍、0.015mmol6,6'-二甲基-2,2'-联吡啶、1mL二氯甲烷、0.8mmol HBpin、0.4mmol重水，然后在双排管中通入氮气磁力搅拌下用油浴加热至30℃，反应15小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:30,v:v)为洗脱剂，柱层析后得纯产品，产率93％。该产品的质谱分析数据如下：理论值，193.1451；实验值，193.1455。1H NMR(400MHz,Chloroform-d)δ7.34–7.29(m,2H),7.25(td,J＝4.3,3.1Hz,3H),5.89(s,1H),4.41(d,J＝5.7Hz,2H),2.21–2.17(m,1.24H),1.66–1.58(m,2H),1.34(dt,J＝15.1,7.4Hz,2H),0.90(t,J＝7.3Hz,3H).13C NMR(101MHz,Chloroform-d)δ173.15,138.53,128.78,127.90,127.56,43.63,36.60,27.94,22.53,13.91.2H NMR(61MHz,)δ7.25,2.20。
实施例9
烯烃转移氢氘化还原产物(2i)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol 1-(吲哚-1-基)戊-4-烯-1-酮、0.012mmol氯化镍、0.015mmol 4,4'-二甲基-2,2'-联吡啶、1mL四氢呋喃、0.8mmol HBpin、0.4mmol重水，然后在双排管中通入氮气磁力搅拌下用油浴加热至30℃，反应15小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:15,v:v)为洗脱剂，柱层析后得纯产品，产率81％。该产品的质谱分析数据如下：理论值，205.1451；实验值，205.1435。1H NMR(400MHz,Chloroform-d)δ8.23(d,J＝8.1Hz,1H),7.20–7.14(m,2H),6.98(td,J＝7.4,1.2Hz,1H),4.03(t,J＝8.5Hz,2H),3.17(t,J＝8.5Hz,2H),2.40(t,J＝7.5Hz,1H),1.74–1.68(m,2H),1.45–1.37(m,2H),0.95(t,J＝7.4Hz,3H).13C NMR(101MHz,Chloroform-d)δ171.61,143.23,131.13,127.62,124.58,123.52,117.07,48.05,35.79,28.11,26.70,22.59,14.07.2H NMR(61MHz)δ7.25,2.41。
实施例10
烯烃转移氢氘化还原产物(2j)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol N-(喹啉-8-基)戊-4-烯酰胺、0.02mmol溴化镍、0.024mmol 4,4'-二甲基-2,2'-联吡啶、1mL四氢呋喃、0.8mmol HBpin、0.4mmol重水，然后在双排管中通入氮气磁力搅拌下用油浴加热至25℃，反应20小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:20,v:v)为洗脱剂，柱层析后得纯产品，产率85％。该产品的质谱分析数据如下：理论值，230.1404；实验值，230.1400。1H NMR(400MHz,Chloroform-d)δ9.80(s,1H),8.83–8.74(m,2H),8.14(dd,J＝8.2,1.7Hz,1H),7.55–7.47(m,2H),7.44(dd,J＝8.3,4.2Hz,1H),2.58–2.53(m,1H),1.85–1.75(m,2H),1.46(dq,J＝14.6,7.3Hz,2H),0.97(t,J＝7.4Hz,3H).13C NMR(101MHz,Chloroform-d)δ172.11,148.22,138.41,136.51,134.64,128.03,127.57,121.70,121.44,116.47,38.13,27.86,22.56,14.00.2H NMR(61MHz,)δ7.24,2.57。
实施例11
烯烃转移氢化还原产物(2k)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol N-苯基戊-4-烯酰胺、0.01mmol碘化镍、0.012mmol 2,2'-联吡啶、1mL二氯甲烷、0.6mmol HBpin、0.4mmol水，然后在双排管中通入氮气磁力搅拌下用油浴加热至20℃，反应10小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:20,v:v)为洗脱剂，柱层析后得纯产品，产率93％。该产品的质谱分析数据如下：理论值，211.1921；实验值，211.1920。1H NMR(400MHz,Chloroform-d)δ5.46(dq,J＝3.7,1.8,1.4Hz,1H),5.42(s,1H),3.32(td,J＝6.9,5.4Hz,2H),2.17(d,J＝7.4Hz,1H),2.14–2.08(m,2H),2.03–1.97(m,2H),1.92(ddt,J＝6.1,4.0,1.9Hz,2H),1.66–1.52(m,6H),1.37–1.30(m,2H),0.91(t,J＝7.4Hz,3H).13C NMR(101MHz,Chloroform-d)δ173.10,134.79,123.65,37.71,37.03,36.70,29.78,28.00,27.88,25.32,22.88,22.44,13.90.2H NMR(61MHz)δ7.26,2.15。
实施例12
烯烃转移氢化还原产物(2l)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol N-(4-乙基苯基)戊-4-烯酰胺、0.012mmol氯化镍、0.015mmol 6,6'-二甲基-2,2'-联吡啶、1mL四氢呋喃、0.8mmol HBpin、0.6mmol水，然后在双排管中通入氮气磁力搅拌下用油浴加热至30℃，反应15小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:20,v:v)为洗脱剂，柱层析后得纯产品，产率87％。该产品的质谱分析数据如下：理论值，207.1608；实验值，207.1622。1H NMR(400MHz,Chloroform-d)δ7.41(d,J＝8.5Hz,2H),7.35(s,1H),7.12(d,J＝8.5Hz,2H),2.59(q,J＝7.5Hz,2H),2.32(t,J＝7.5Hz,1.14H),1.72–1.65(m,2H),1.42–1.34(m,2H),1.19(t,J＝7.5Hz,3H),0.92(t,J＝7.3Hz,3H).13C NMR(101MHz,Chloroform-d)δ171.54,140.32,135.71,128.36,120.11,37.57,28.38,27.85,27.79,22.49,22.45,15.77,13.92.2H NMR(61MHz,)δ7.26,2.34。
实施例13
烯烃转移氢化还原产物(2q)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol 4-甲基-N-苯基戊-3-烯酰胺、0.014mmol溴化镍、0.017mmol 6,6'-二甲基-2,2'-联吡啶、1mL四氢呋喃、1.0mmol HBpin、0.6mmol水，然后在双排管中通入氮气磁力搅拌下用油浴加热至30℃，反应24小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:10,v:v)为洗脱剂，柱层析后得纯产品，产率88％。该产品的质谱分析数据如下：理论值，193.1451；实验值，193.1450。1H NMR(400MHz,Chloroform-d)δ7.50(d,J＝7.4Hz,2H),7.34–7.26(m,3H),7.08(t,J＝7.4Hz,1H),2.35(s,1.23H),1.66–1.56(m,3H),0.92(d,J＝6.5Hz,6H).13C NMR(101MHz,Chloroform-d)δ171.77,138.06,129.09,124.27,119.86,35.95,34.50,27.90,22.45.2H NMR(61MHz,)δ7.26,2.35。
实施例14
烯烃转移氢化还原产物(2r)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol N-((1R，4aS，10aR)-7-异丙基-1,4a-二甲基-1,2,3,4,4a，9,10,10a-八氢菲-1-基)甲基)戊-4-烯酰胺、0.02mmol溴化镍、0.024mmol4,4'-二叔丁基-2,2'-联吡啶、1mL四氢呋喃、1.2mmol HBpin、0.8mmol水，然后在双排管中通入氮气磁力搅拌下用油浴加热至40℃，反应12小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:20,v:v)为洗脱剂，柱层析后得纯产品，产率80％。该产品的质谱分析数据如下：理论值，371.3173；实验值，371.3205。1H NMR(400MHz,Chloroform-d)δ7.16(d,J＝8.2Hz,1H),6.98(d,J＝8.1Hz,1H),6.89(s,1H),5.44(s,1H),3.24–3.07(m,2H),2.96–2.74(m,3H),2.30–2.25(m,1.13H),2.17–2.12(m,1H),1.86–1.55(m,6H),1.43–1.27(m,6H),1.23–1.20(m,9H),0.92(s,3H),0.87(t,J＝7.3Hz,3H).13C NMR(101MHz,Chloroform-d)δ173.41,147.26,145.76,134.89,127.05,124.26,123.96,49.77,45.41,38.44,37.52,37.37,36.92,36.29,33.52,30.29,27.98,25.39,24.10,22.52,19.02,18.82,18.69,13.89。
实施例15
烯烃转移氢化还原产物(3a)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol N-苯基戊-4-烯酰胺、0.01mmol氯化镍、0.012mmol 6,6'-二甲基-2,2'-联吡啶、1mL二氯甲烷、0.8mmol HBpin、0.4mmol水，然后在双排管中通入氮气磁力搅拌下用油浴加热至30℃，反应15小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:30,v:v)为洗脱剂，柱层析后得纯产品，产率92％。该产品的质谱分析数据如下：理论值，178.1232；实验值，178.1255。1H NMR(400MHz,Chloroform-d)δ7.52(d,J＝7.8Hz,2H),7.44(s,1H),7.30(t,J＝7.9Hz,2H),7.12–7.06(m,1H),2.35(t,J＝7.6Hz,2H),1.70(p,J＝7.5Hz,2H),1.39(q,J＝7.5Hz,2H),0.93(t,J＝7.4Hz,3H).13C NMR(101MHz,Chloroform-d)δ171.73,138.11,129.05,124.24,119.94,37.62,27.81,22.48,13.92。
实施例16
烯烃转移氢化还原产物(3o)的制备：在氮气氛围中，向10ml的反应瓶中加入0.2mmol 1-(3,4-二氢喹啉-1(2H)-基)戊-4-烯-1-酮、0.012mmol溴化镍、0.015mmol 4,4'-二叔丁基-2,2'-联吡啶、1mL四氢呋喃、1.2mmolHBpin、0.6mmol水，然后在双排管中通入氮气磁力搅拌下用油浴加热至50℃，反应20小时。去掉油浴，向反应液加1mL水终止反应，用2mL的乙酸乙酯萃取三次，合并有机相并用无水MgSO4干燥30分钟，过滤；滤液用旋转蒸发器浓缩，浓缩后用乙酸乙酯和石油醚(1:10,v:v)为洗脱剂，柱层析后得纯产品，产率86％。该产品的质谱分析数据如下：理论值，218.1545；实验值，218.1540。1H NMR(400MHz,Chloroform-d)δ7.23–7.01(m,4H),3.77(t,J＝6.6Hz,2H),2.69(t,J＝6.7Hz,2H),2.50–2.45(m,2H),1.93(t,J＝6.7Hz,2H),1.61(q,J＝7.7Hz,2H),1.28(s,2H),0.87–0.80(m,3H).13CNMR(101MHz,Chloroform-d)δ173.30,139.34,128.54,126.13,125.28,124.77,42.90,34.34,28.15,26.92,24.28,22.53,13.98。

Claims (9)

1.一种“链行走”式烯烃转移氢化或氘化的还原方法，步骤为：将烯烃衍生物、还原剂、水或重水、镍源和配体均加到极性溶剂中，置于反应器内，加热，经柱层析获得还原产物；
烯烃的结构式为：
Figure FDA0003624827350000011
转移氢氘化或氢化产物结构式为：
Figure FDA0003624827350000012
其中R1＝芳基或烷基基团和R2＝芳基或烷基基团。
2.根据权利要求1所述的一种“链行走”式烯烃转移氢化或氘化的还原方法，其特征在于：反应过程中采用TLC薄层色谱跟踪反应进程。
3.根据权利要求1所述的一种“链行走”式烯烃转移氢化或氘化的还原方法，其特征在于：烯烃衍生物、还原剂、镍源、配体、水(或重水)的摩尔比为1：3～6.0：0.02～0.10：0.024～0.12：2～4.0。
4.根据权利要求1所述的一种“链行走”式烯烃转移氢化或氘化的还原方法，其特征在于：所述还原剂为频哪醇硼烷或者三乙氧基硅烷。
5.根据权利要求1所述的一种“链行走”式烯烃转移氢化或氘化的还原方法，其特征在于：所述镍源为溴化镍、碘化镍、氯化镍中的一种或多种。
6.根据权利要求1所述的一种“链行走”式烯烃转移氢化或氘化的还原方法，其特征在于：配体为2,2'-联吡啶、6,6'-二甲基-2,2'-联吡啶、4,4'-二叔丁基-2,2'-联吡啶中的一种或多种。
7.根据权利要求1所述的一种“链行走”式烯烃转移氢化或氘化的还原方法，其特征在于：极性溶剂为二氯甲烷或者四氢呋喃。
8.根据权利要求1所述的一种“链行走”式烯烃转移氢化或氘化的还原方法，其特征在于：反应温度为20℃～50℃。
9.根据权利要求1所述的一种“链行走”式烯烃转移氢化或氘化的还原方法，其特征在于：反应时间10-24小时。
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