CN109020864B - 金属氢化物/钯化合物催化还原体系在烯基活泼亚甲基化合物还原中的应用及还原方法 - Google Patents

金属氢化物/钯化合物催化还原体系在烯基活泼亚甲基化合物还原中的应用及还原方法 Download PDF

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CN109020864B
CN109020864B CN201811064127.4A CN201811064127A CN109020864B CN 109020864 B CN109020864 B CN 109020864B CN 201811064127 A CN201811064127 A CN 201811064127A CN 109020864 B CN109020864 B CN 109020864B
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张士磊
毛玉健
刘晔
桂晶晶
陈韶华
胡延维
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Zhangjiagang Industrial Technology Research Institute Of Suzhou University
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Abstract

本发明公开了金属氢化物/钯化合物催化还原体系在烯基活泼亚甲基化合物还原中的应用及还原方法，反应包括以下步骤，以烯基活泼亚甲基化合物为底物、金属氢化物为还原剂、钯化合物为催化剂，还原反应，得到还原产物，完成烯基活泼亚甲基化合物的还原。本发明的还原体系是还原烯基活泼亚甲基化合物的简易方法，所用的氢化物和钯化合物催化剂都是实验室中容易获得的试剂，相比于常用的氢气氢化方法和还原剂还原方法，此方法更易操作，安全性更高，条件温和，反应收率高，而且可以一锅两步反应，具有很高的原子经济性和步骤经济性。

Description

金属氢化物/钯化合物催化还原体系在烯基活泼亚甲基化合 物还原中的应用及还原方法
技术领域
本发明属于有机合成技术领域，具体涉及金属氢化物/钯化合物催化体系在烯基活泼亚甲基化合物还原及一锅反应中的应用。
背景技术
氢化钠是一种实验室及工业上经常使用的强碱，长期以来，很少有做为还原剂被使用的相关报道，而且现有反应需要大大过量的还原剂(3当量)，同时需要至少2当量的碘化钠做为促进剂。烯基活泼亚甲基化合物的还原是一种常见的化学转化，生成相应的单烷基取代的活泼亚甲基化合物；这类反应一般是使用氢气/钯碳条件进行还原；另外，一些氢负试剂，比如[(Ph3P)CuH]6 (Stryker试剂)、R3SiH、Hantzsch 酯等也可以完成这种缺电子双键的还原。但是，这些还原条件要么具有一定的危险性，比如易***的氢气；要么试剂较贵、反应缺乏原子经济性并且反应后需要处理较多的废弃物，比如[(Ph3P)CuH]6 (Stryker试剂)、R3SiH、Hantzsch 酯等，或者有些反应后需要处理大量废水，所以在工业应用上也有一定的局限性。
发明内容
本发明要解决的技术问题是提供一种金属氢化物/钯化合物催化还原体系的应用，从而提供一种烯基活泼亚甲基化合物还原的新方法，以及此方法在一锅反应中的应用。
本发明实现以上提及的还原烯基活泼亚甲基化合物的技术手段是以金属氢化物为还原剂，钯及其盐类为催化剂，在溶剂中反应得到双键还原的产物。具体技术方案如下：
金属氢化物/钯化合物催化还原体系在烯基活泼亚甲基化合物还原中的应用。
烯基活泼亚甲基化合物还原的方法，以烯基活泼亚甲基化合物为底物、金属氢化物为还原剂、钯化合物为催化剂，还原反应，得到还原产物，完成烯基活泼亚甲基化合物的还原。
上述技术方案中，还原反应后，加入饱和氯化铵水溶液中止反应，然后经过萃取、干燥、旋蒸、柱层析纯化得到还原产物。
本发明中，烯基活泼亚甲基化合物的化学结构式如下：
Figure DEST_PATH_IMAGE001
其中，R1、R2独立的选自氢、烷基、苯基、取代苯基、萘基、吡啶基、喹啉基。
烯基活泼亚甲基化合物的化学结构式中，烷基可以为甲基，取代苯基可以为卤素取代苯基、甲氧基取代苯基。
本发明中，所述金属氢化物包括氢化钠、氢化锂、氢化钾、氢化钙，优选氢化钠、氢化锂，更优选氢化钠；所述钯化合物包括为氯化钯、醋酸钯、Pd(MeCN)2Cl2、[(η3-C3H5)PdCl]2、Pd(TFA)2、Pd(dppp)Cl2、Pd2(dba)3、Pd(C6H5CN)2Cl2、Pd(OH)2、Pd/C、Pd(PPh3)4、Pd(PPh3)2Cl2，优选氯化钯、醋酸钯，更优选氯化钯。
本发明中，所述钯化合物、金属氢化物、烯基活泼亚甲基化合物的摩尔比为(0.01～1) ∶(1～5) ∶1，优选为(0.03～0.1) ∶(1～3) ∶1，更优选为0.05∶(1.5～2.5) ∶1，最优选为0.05∶2∶1。
本发明中，烯基活泼亚甲基化合物的还原在氮气气氛下、溶剂中进行；所述溶剂包括DMA(N,N-二甲基乙酰胺)、DMF、THF、DME或者二氧六环。
本发明中，烯基活泼亚甲基化合物还原的温度为-50℃～120℃，优选0～50℃，更优选室温；还原的时间为0.3～10小时，优选0.4～5小时，更优选0.5小时。
本发明氢化钠/钯还原烯基活泼亚甲基化合物有以下几点优势：1）相比于硼氢化钠，氢化钠价格更加便宜（工业上硼氢化钠是以氢化钠为原料制备的）；相比于氢气/钯碳还原，氢化钠方法的安全性更高；2）氢化钠分子量小而且组成简单，反应中使用量少，所以用氢化钠做为还原剂是一种原子经济的方法；副产物除了无害的钠盐，没有其它废物产生；3）烯基活泼亚甲基化合物被氢化钠还原后的产物在后处理前是钠盐，这一点和现有的还原方法都不一样，具有反应活性的钠盐可以继续和亲电试剂反应，得到二取代的产物，拓展了烯基活泼亚甲基化合物的应用。并且在此一锅反应中，氢化钠的还原性和碱性都被充分利用，大大提高了反应的原子经济性和步骤经济性，降低了反应成本。
本发明的技术方案具体可以如下所述：氮气保护下，把钯化合物和金属氢化物悬浮于溶剂中搅拌，然后加入底物烯基活泼亚甲基化合物，在-50℃至120℃下反应0.3～10小时，加入饱和氯化铵水溶液中止反应，用溶剂萃取，蒸干，柱层析纯化，得到产物。
烯基活泼亚甲基化合物的还原是有机合成中经常使用的化学反应，一般采用两类方法：一类是使用氢气/钯碳进行氢化还原，在这个过程中，氢气的使用是一个潜在的危险因素，操作不当就会引起着火、***；另一类是使用还原剂进行还原，价格较高且需要处理大量废水。本发明使用相对比较安全且价格低廉的金属氢化物代替氢气和还原剂用于烯基活泼亚甲基化合物的还原具有重要的意义；而且更重要的是，此方法充分发挥了氢化钠的还原性和碱性，可以进行一锅反应。
本发明的还原体系是还原烯基活泼亚甲基化合物的简易方法，所用的氢化物和钯化合物催化剂都是实验室中容易获得的试剂，相比于常用的氢气氢化方法和还原剂还原方法，此方法更易操作，安全性更高，条件温和，反应收率高，而且可以一锅两步反应，具有很高的原子经济性和步骤经济性。
具体实施方式
实施例1
Figure 47033DEST_PATH_IMAGE002
氮气保护下，氯化钯 (1.7 mg, 0.01 mmol, 5 mol%)和氢化钠 (60% in oil, 16mg, 0.4 mmol, 2 equiv)悬浮于DMA (1.0 mL)，室温搅拌5分钟，加入化合物1a (0.2mmol)在 DMA (0.5 mL)的溶液，然后在室温反应30分钟，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2a，收率99%。1H NMR (400 MHz, CDCl3): δ 7.48 (t, J = 7.6 Hz, 2H), 7.38 (t, J = 7.3 Hz,1H), 7.25-7.17 (m, 5H), 7.17-7.10 (m, 3H), 7.02-6.93 (m, 2H), 6.64 (d, J =7.8 Hz, 1H), 3.95-3.88 (m, 1H), 3.52 (dd, J = 13.5, 4.2 Hz, 1H), 3.17 (dd, J= 13.5, 8.2 Hz, 1H). 13C NMR (151 MHz, CDCl3): δ 176.56, 144.51, 137.40,134.57, 129.71, 128.31, 128.23, 128.18, 127.99, 126.83, 126.78, 124.83,122.63, 47.36, 37.26. LR-MS (ESI): m/z 300.2 [M+H]+。
Figure DEST_PATH_IMAGE003
氮气保护下，氯化钯 (1.7 mg, 0.01 mmol, 5 mol%)和氢化钠 (60% in oil, 16mg, 0.4 mmol, 2 equiv)悬浮于DMA (1.0 mL)，室温搅拌5分钟，加入化合物1a (0.2mmol)在 DMA (0.5 mL)的溶液，然后在室温反应30分钟，加入溴化苄（1.5eq.），继续搅拌反应，待原料反应完后，加饱和氯化铵水溶液淬灭反应，用乙酸乙酯萃取，收集有机相，旋干溶剂得到粗产物，柱层析，最终得到化合物3a，收率98%。1H NMR (400 MHz, CDCl3): δ 7.38-7.27 (m, 4H), 7.13-7.04 (m, 7H), 7.02-6.94 (m, 5H), 6.64 (d, J = 7.3 Hz, 2H),6.21 (d, J = 7.7 Hz, 1H), 3.47 (d, J = 12.9 Hz, 2H), 3.25 (d, J = 12.9 Hz,2H). 13C NMR (151 MHz, CDCl3): δ 177.80, 144.12, 136.08, 134.37, 130.26,130.14, 129.49, 128.06, 127.85, 127.76, 126.81, 126.65, 124.42, 122.23,108.88, 56.67, 43.83. LR-MS (ESI): m/z 390.3 [M+H]+。
实施例2
Figure 317608DEST_PATH_IMAGE004
氮气保护下，醋酸钯 (2.2 mg, 0.01 mmol, 5 mol%)和氢化锂 (4.8 mg, 0.6mmol, 3.0 equiv)悬浮于DMF (1.0 mL)，室温搅拌5分钟，加入化合物1a (0.2 mmol)在DMF (0.5 mL)的溶液，然后在120℃反应0.5小时，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2a，收率92%。
实施例3
Figure DEST_PATH_IMAGE005
氮气保护下，Pd2(dba)3 (1.8 mg, 0.002 mmol, 1 mol%)和氢化钾 (30% in oil,133 mg, 1.0 mmol, 5 equiv)悬浮于THF (1.0 mL)，室温搅拌5分钟，加入化合物1a (0.2mmol)在 THF (0.5 mL)的溶液，然后在-50℃反应10小时，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2a，收率71%。
实施例4
Figure 21995DEST_PATH_IMAGE006
氮气保护下，Pd(TFA)2 (67 mg, 0.2 mmol, 100 mol%)和氢化钙 (16 mg, 0.4mmol, 2.0 equiv)悬浮于DME (1.0 mL)，室温搅拌5分钟，加入化合物1a (0.2 mmol)在DME (0.5 mL)的溶液，然后在90℃反应0.5小时，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2a，收率83%。
实施例5
Figure DEST_PATH_IMAGE007
氮气保护下，[(η3-C3H5)PdCl]2 (1.4 mg, 0.004 mmol, 2 mol%)和氢化钠(60%in oil, 8 mg, 0.20 mmol, 1.0 equiv)悬浮于二氧六环 (1.0 mL)，室温搅拌5分钟，加入化合物1a (0.2 mmol)在二氧六环 (0.5 mL)的溶液，然后在30℃反应2小时，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2a，收率69%。
实施例6
Figure 719824DEST_PATH_IMAGE008
氮气保护下，Pd/C (10%, 0.01 mmol, 5 mol%)和氢化钠 (60% in oil, 16 mg,0.4 mmol, 2 equiv)悬浮于DMA (1.0 mL)，室温搅拌5分钟，加入化合物1a (0.2 mmol)在DMA (0.5 mL)的溶液，然后在室温反应10小时，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2a，收率8%。
实施例7
Figure DEST_PATH_IMAGE009
氮气保护下，Pd(dppp)Cl2 (6 mg, 0.01 mmol, 5 mol%)和氢化钠 (60% in oil,16 mg, 0.4 mmol, 2 equiv)悬浮于DMA (1.0 mL)，室温搅拌5分钟，加入化合物1a (0.2mmol)在 DMA (0.5 mL)的溶液，然后在室温反应1小时，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2a，收率57%。
实施例8
Figure 596644DEST_PATH_IMAGE010
氮气保护下，Pd(C6H5CN)2Cl2 (3.8 mg, 0.01 mmol, 5 mol%)和氢化钠 (60% inoil, 16 mg, 0.4 mmol, 2 equiv)悬浮于DMA (1.0 mL)，室温搅拌5分钟，加入化合物1a(0.2 mmol)在 DMA (0.5 mL)的溶液，然后在室温反应1小时，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2a，收率62%。
实施例9
Figure DEST_PATH_IMAGE011
氮气保护下，Pd(OH)2 (1.4 mg, 0.01 mmol, 5 mol%)和氢化钠 (60% in oil,16 mg, 0.4 mmol, 2 equiv)悬浮于DMA (1.0 mL)，室温搅拌5分钟，加入化合物1a (0.2mmol)在 DMA (0.5 mL)的溶液，然后在室温反应0.5小时，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2a，收率71%。
实施例10
Figure 467648DEST_PATH_IMAGE012
氮气保护下，氯化钯 (1.7 mg, 0.01 mmol, 5 mol%)和氢化钠 (60% in oil, 16mg, 0.4 mmol, 2 equiv)悬浮于DMA (1.0 mL)，室温搅拌5分钟，加入化合物1b (0.2mmol)在 DMA (0.5 mL)的溶液，然后在室温反应30分钟，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2b，收率98%。1H NMR (400 MHz, CDCl3): δ 7.49 (t, J = 7.6 Hz, 2H), 7.39 (t, J = 7.4 Hz,1H), 7.22 (d, J = 7.6 Hz, 2H), 7.19-7.11 (m, 2H), 7.03-6.96 (m, 2H), 6.80-6.74 (m, 2H), 6.69-6.64 (m, 2H), 3.97-3.88 (m, 1H), 3.69 (s, 3H), 3.51 (dd, J= 13.5, 4.1 Hz, 1H), 3.13 (dd, J = 13.4, 8.4 Hz, 1H). 13C NMR (101 MHz,CDCl3): δ 176.56, 159.52, 144.52, 138.98, 134.57, 129.71, 129.30, 128.28,128.19, 128.00, 126.78, 124.87, 122.64, 122.14, 114.69, 112.86, 109.34,55.26, 47.28, 37.34. LR-MS (ESI): m/z 330.2 [M+H]+。
实施例11
Figure DEST_PATH_IMAGE013
氮气保护下，氯化钯 (1.7 mg, 0.01 mmol, 5 mol%)和氢化钠 (60% in oil, 16mg, 0.4 mmol, 2 equiv)悬浮于DMA (1.0 mL)，室温搅拌5分钟，加入化合物1c (0.2mmol)在 DMA (0.5 mL)的溶液，然后在室温反应30分钟，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2c，收率98%。1H NMR (400 MHz, CDCl3): δ 7.49 (t, J = 7.5 Hz, 2H), 7.38 (t, J = 7.3 Hz,1H), 7.31 (d, J = 7.7 Hz, 2H), 7.25-7.17 (m, 2H), 7.12 (t, J = 7.6 Hz, 1H),7.08-6.91 (m, 3H), 6.89 (d, J = 7.2 Hz, 1H), 6.69 (d, J = 7.8 Hz, 1H), 3.98-3.90 (m, 1H), 3.60 (dd, J = 13.8, 5.0 Hz, 1H), 3.12 (dd, J = 13.7, 8.4 Hz,1H). 13C NMR (101 MHz, CDCl3): δ 176.44, 161.37 (d, J = 246.0 Hz), 144.30,134.59, 131.76 (d, J = 4.5 Hz), 129.72, 128.72 (d, J = 8.1 Hz), 128.18,128.04, 127.94, 126.74, 125.07, 124.92, 124.02 (d, J = 3.6 Hz), 122.69,115.47 (d, J = 22.2 Hz), 109.26, 46.05, 30.26. LR-MS (ESI): m/z 318.3 [M+H]+。
实施例12
Figure 743384DEST_PATH_IMAGE014
氮气保护下，氯化钯 (1.7 mg, 0.01 mmol, 5 mol%)和氢化钠 (60% in oil, 16mg, 0.4 mmol, 2 equiv)悬浮于DMA (1.0 mL)，室温搅拌5分钟，加入化合物1d (0.2mmol)在 DMA (0.5 mL)的溶液，然后在室温反应1小时，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2d，收率97%。1H NMR (400 MHz, CDCl3): δ 7.84-7.77 (m, 1H), 7.77-7.70 (m, 2H), 7.62 (s,1H), 7.49-7.41 (m, 4H), 7.40-7.31 (m, 2H), 7.20 (d, J = 7.5 Hz, 2H), 7.14-7.07 (m, 1H), 6.97-6.91 (m, 2H), 6.64 (d, J = 7.8 Hz, 1H), 4.02 (dd, J = 8.2,4.4 Hz, 1H), 3.70 (dd, J = 13.6, 4.3 Hz, 1H), 3.32 (dd, J = 13.6, 8.4 Hz,1H). 13C NMR (151 MHz, CDCl3): δ 176.60, 144.44, 135.12, 134.54, 133.44,132.46, 129.68, 128.31, 128.20, 128.15, 128.01, 127.96, 127.87, 127.77,127.71, 126.74, 126.09, 125.67, 124.88, 122.65, 109.36, 47.28, 37.41. LR-MS(ESI): m/z 350.2 [M+H]+。
实施例13
Figure DEST_PATH_IMAGE015
氮气保护下，氯化钯 (1.7 mg, 0.01 mmol, 5 mol%)和氢化钠 (60% in oil, 16mg, 0.4 mmol, 2 equiv)悬浮于DMA (1.0 mL)，室温搅拌5分钟，加入化合物1e (0.2mmol)在 DMA (0.5 mL)的溶液，然后在室温反应30分钟，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2e，收率98%。1H NMR (400 MHz, CDCl3): δ 8.86 (d, J = 4.1 Hz, 1H), 8.27 (d, J = 8.3 Hz,1H), 8.20 (d, J = 8.4 Hz, 1H), 7.76 (t, J = 7.5 Hz, 1H), 7.63 (t, J = 7.5 Hz,1H), 7.53 (t, J = 7.6 Hz, 2H), 7.42 (t, J = 7.3 Hz, 1H), 7.35 (d, J = 7.7 Hz,2H), 7.31 (d, J = 4.1 Hz, 1H), 7.16 (t, J = 7.7 Hz, 1H), 6.91 (t, J = 7.5 Hz,1H), 6.77 (d, J = 7.9 Hz, 1H), 6.71 (d, J = 7.3 Hz, 1H), 4.16-4.02 (m, 2H),3.36 (dd, J = 13.5, 9.5 Hz, 1H). 13C NMR (151 MHz, CDCl3): δ 176.17, 149.67,148.34, 144.70, 144.23, 134.37, 130.28, 129.80, 129.74, 128.37, 128.35,127.85, 127.44, 127.11, 126.65, 124.99, 123.76, 122.82, 122.47, 109.67 ,45.71, 34.03. LR-MS (ESI): m/z 351.1 [M+H]+。
实施例14
Figure 612114DEST_PATH_IMAGE016
氮气保护下，氯化钯 (1.7 mg, 0.01 mmol, 5 mol%)和氢化钠 (60% in oil, 16mg, 0.4 mmol, 2 equiv)悬浮于DMA (1.0 mL)，室温搅拌5分钟，加入化合物1f (0.2mmol)在 DMA (0.5 mL)的溶液，然后在室温反应30分钟，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2f（Diastereomer a/b = 58/42），收率96%。Diastereomer a: 1H NMR (400 MHz, CDCl3): δ7.46 (t, J = 7.6 Hz, 2H), 7.36 (t, J = 7.4 Hz, 1H), 7.32-7.17 (m, 7H), 7.09(t, J = 7.6 Hz, 1H), 6.89 (t, J = 7.4 Hz, 1H), 6.69-6.60 (m, 2H), 3.88-3.84(m, 1H), 3.83-3.77 (m, 1H), 1.31 (d, J = 7.0 Hz, 3H). 13C NMR (151 MHz,CDCl3): δ 176.26, 144.85, 142.41, 134.63, 129.71, 128.34, 128.17, 128.06,127.95, 126.85, 126.77, 126.66, 125.05, 122.46, 109.12, 52.58, 40.72, 14.32.Diastereomer b: 1H NMR (400 MHz, CDCl3): δ 7.40 (t, J = 7.4 Hz, 2H), 7.34 (d,J = 7.2 Hz, 2H), 7.18-7.09 (m, 4H), 7.05 (t, J = 7.4 Hz, 1H), 6.98 (d, J =6.6 Hz, 2H), 6.92 (d, J = 7.5 Hz, 2H), 6.51 (d, J = 7.7 Hz, 1H), 3.79 (d, J =4.4 Hz, 1H), 3.75-3.65 (m, 1H), 1.69 (d, J = 7.2 Hz, 3H). 13C NMR (151 MHz,CDCl3): δ 176.24, 144.97, 141.21, 134.45, 129.61, 128.25, 128.14, 128.11,127.90, 127.03, 126.97, 126.85, 125.23, 122.37, 109.22, 52.49, 42.51, 19.22.LR-MS (ESI): m/z 314.2 [M+H]+。
实施例15
Figure DEST_PATH_IMAGE017
氮气保护下，氯化钯 (1.7 mg, 0.01 mmol, 5 mol%)和氢化钠 (60% in oil, 16mg, 0.4 mmol, 2 equiv)悬浮于DMA (1.0 mL)，室温搅拌5分钟，加入化合物1g (0.2mmol)在 DMA (0.5 mL)的溶液，然后在室温反应30分钟，加入饱和氯化铵水溶液中止反应，用乙酸乙酯萃取，合并萃取液，用硫酸钠干燥，旋蒸蒸干，柱层析纯化，得到产物2g，收率98%。1H NMR (400 MHz, CDCl3): δ 7.52 (t, J = 7.6 Hz, 2H), 7.44-7.31 (m, 4H),7.20 (t, J = 7.7 Hz, 1H), 7.08 (t, J = 7.4 Hz, 1H), 6.79 (d, J = 7.8 Hz, 1H),3.55 (d, J = 2.7 Hz, 1H), 2.66-2.54 (m, 1H), 1.18 (d, J = 7.0 Hz, 3H), 0.97(d, J = 6.8 Hz, 3H). 13C NMR (151 MHz, CDCl3): δ 176.91, 144.85, 134.72,129.70, 128.09, 127.81, 127.67, 126.77, 124.73, 122.64, 109.22, 51.76, 31.48,19.90, 18.06. LR-MS (ESI): m/z 252.2 [M+H]+。

Claims (3)

1.金属氢化物/钯化合物催化还原体系在烯基活泼亚甲基化合物还原中的应用；所述烯基活泼亚甲基化合物的化学结构式如下：
Figure DEST_PATH_IMAGE002
其中，R1、R2独立的选自氢、烷基、苯基、取代苯基、萘基、吡啶基、喹啉基；
所述金属氢化物为氢化钠、氢化锂、氢化钾或者氢化钙；所述钯化合物为氯化钯、醋酸钯、Pd(dppp)Cl2、或者Pd(OH)2。
2. 根据权利要求1所述的应用，其特征在于，所述钯化合物、金属氢化物、烯基活泼亚甲基化合物的摩尔比为(0.01～1) ∶(1～5) ∶1。
3.根据权利要求1所述的应用，其特征在于，烯基活泼亚甲基化合物的还原在氮气气氛下、溶剂中进行；烯基活泼亚甲基化合物还原的温度为-50℃～120℃，还原的时间为0.3～10小时。
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