单氢钌配合物的合成及其催化氢化中的应用
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摘要
利用含[Ru]-H键的过渡金属钌配合物催化氢化不饱和化合物已成为有机金属化学里的一个热门课题,其关键就在于如何设计与运用高活性配体。本文对钌配合物催化氢化烯烃的主要反应类型,和含有手性二胺、手性磷配体配合物的合成及其在催化氢化中的应用进行了综述。
本文的研究工作包括:
1.分别研究了在无水THF、H_2O/THF、ROH/THF和CH_3CN/THF条件下配合物TpRuH(PPh_3)(CH_3CN)[Tp=Hydrotris(pyrazolyl)borate]催化氢化烯烃的反应,发现向干燥THF体系中添加微量小分子H_2O、CH_3CN或ROH(R=Me,Et,iso-propyl and tert-butyl)时对催化氢化反应具有显著的促进作用。催化机理研究表明,添加物先取代配合物的PPh_3配体生成TpRuH(CH_3CN)L(L=H_2O,CH_3CN or ROH),降低空间位阻,烯烃随即取代一个配体形成配合物TpRuH(olefin)L(L=H_2O,CH_3CN or ROH),然后H。转移到烯烃的碳原子上,留下一个空位置,一分子H_2配位到空位置后形成[Ru]-η~2-H_2络合物,η~2-H_2配体发生裂解,脱掉一分子的烷烃,并重新生成有一个空位的[Ru]-H中间体。在无添加物的条件下,由于PPh_3配体的空间障碍,烯烃难以与TpRuH(PPh_3)(CH_3CN)反应生成TpRuH(olefin)L,影响到催化循环的进行;在醇存在时,随着醇的位阻逐渐增加而转化率降低。
2.研究了二苯基乙二胺的合成工艺。探讨了碱催化剂对合成2,4,5一三苯基咪唑啉的影响,结果表明强碱性有利于提高环化产率,最终选定异丙醇钠为催化剂;分别比较了浓度为40%和48%的氢溴酸在不同时间对水解(士)-N-乙酰-N'-苯甲酰-1,2-乙二胺的影响,得到最佳反应条件是氢溴酸浓度为48%,水解时间为25 h;研究了不同pH值下二苯基乙二胺氢溴酸盐和二苯基乙二胺酒石酸盐的中和效果,发现以KOH调节水溶液至pH=12-14时水解产率最高。
3.以(R,R)-1,2-二苯基乙二胺和Tp为配体,合成了一种新的单氢钌配合物TpRu(PPh_3)(η~1-PhCHNH_2CHNH_2Ph)H结构经IR、EA、~1H NMR和(31)~PNMR确证。用该催化剂催化氢化前手性酮时,发现其对位阻较小的脂肪族酮的催化氢化作用较明显。但由于配体η~1-PhCHNH_2CHNH_2Ph上N-Cσ-键容易发生自由旋转,所以该化合物对前手性酮的氢化还原不具有不对称催化作用。
Hydrogenation of unsaturated compounds catalyzed by Ruthenium(Ⅱ) complexes with[Ru]-H bond has been widely investigated.The research emphasis focuses on how to desgin ligands to synthesize the reactive complexes.In this thesis,the main types of catalytic hydrogenation of olefins and synthesis of complexes of chiral diamines and chiral phosphorus ligands are reviewed.
The main work can be summarized as follows:
1.Hydrogenation of olefins catalyzed by TpRuH(PPh_3)(CH_3CN) [Tp=Hydrotris(pyrazoly1)borate]in anhydrous THF,H_2O/THF, CH_3CN/THF and ROH/THF(R=Me,Et,iso-propy1 and tert-buty1) has been studied,respectively.The remarkable promoting effect was found in the present of additives,such as H_2O,CH_3CN and ROH.A catalytic mechanism is proposed.The PPh_3 ligand in TpRuH(CH_3CN)L(L=H_2O,CH_3CN or ROH) is first replaced by the additive to reduce the steric hinderance,and then olefin replaces a ligand to form a complex TpRuH(olefin)L(L=H_2O, CH_3CN or ROH).The hydride ligand of TpRuH(olefin)L is transferred to the coordinated olefin and H2 is then coordinated to the formed vacant position to generate a complex withη~2-H_2 ligand.The metathesis reaction ofη~2-H_2 occurs,it transfers a hydrogen proton to the coordinated olefin to form a alkane,and regenerate an intermediate with Ru-H bond.Due to the steric hindrance of PPh3,it is difficult for olefin to react with TpRuH(PPh_3)(CH_3CN) in the absence of the additives,which is unfavorable for the catalytic hydrogenation.The turnover decreases with the increased steric hindrance of alcohols.
2.The synthetic techniques of diphenylethanediamine were studied. Effect of base as catalyst on the preparation of 2,4,5-triphenylimidazoline was studied and it was found that strong base is favorable for cyclization. Sodium isopropoxide is finally selected as the catalyst for this cyclization. Hydrolysis time of(±)-N-acety1-N'-benzoy1-1,2-ethylenediamine under the condition of 40%and 48%HBr was also studied.The optimizational hydrolysis concentration of HBr is 48%and hydrolytic time is 25h.Effect of pH value on the neutralization of diphenylethylenediamine hydrobromide and diphenylethylenediamine tartrate was studied.Using KOH to adjust the pH value of aqueous solution to 12-14 resulted in the highest yield.
3.A novel hydride complex TpRu(PPh_3)(η~1-PhCHNH_2CHNH_2Ph)H was synthesized using Tp and(R,R)-1,2-diphenylethanediamine as ligand, which was confirmed by IR spectroscopy,EA,~1H and ~(31)P NMR spectra. Althrough this complex was found to be reactive to catalytic hydrogenation of some ketones and esters,no chiral products were detected by ~1H NMR spectrum.Due to free rotation of the N-C -bond in the ligandη~1-PhCHNH_2CHNH_2Ph,this newly synthesized complex has no unsymetric catalytic reactivity to hydrogenation of prochiral ketones.
本文的研究工作包括:
1.分别研究了在无水THF、H_2O/THF、ROH/THF和CH_3CN/THF条件下配合物TpRuH(PPh_3)(CH_3CN)[Tp=Hydrotris(pyrazolyl)borate]催化氢化烯烃的反应,发现向干燥THF体系中添加微量小分子H_2O、CH_3CN或ROH(R=Me,Et,iso-propyl and tert-butyl)时对催化氢化反应具有显著的促进作用。催化机理研究表明,添加物先取代配合物的PPh_3配体生成TpRuH(CH_3CN)L(L=H_2O,CH_3CN or ROH),降低空间位阻,烯烃随即取代一个配体形成配合物TpRuH(olefin)L(L=H_2O,CH_3CN or ROH),然后H。转移到烯烃的碳原子上,留下一个空位置,一分子H_2配位到空位置后形成[Ru]-η~2-H_2络合物,η~2-H_2配体发生裂解,脱掉一分子的烷烃,并重新生成有一个空位的[Ru]-H中间体。在无添加物的条件下,由于PPh_3配体的空间障碍,烯烃难以与TpRuH(PPh_3)(CH_3CN)反应生成TpRuH(olefin)L,影响到催化循环的进行;在醇存在时,随着醇的位阻逐渐增加而转化率降低。
2.研究了二苯基乙二胺的合成工艺。探讨了碱催化剂对合成2,4,5一三苯基咪唑啉的影响,结果表明强碱性有利于提高环化产率,最终选定异丙醇钠为催化剂;分别比较了浓度为40%和48%的氢溴酸在不同时间对水解(士)-N-乙酰-N'-苯甲酰-1,2-乙二胺的影响,得到最佳反应条件是氢溴酸浓度为48%,水解时间为25 h;研究了不同pH值下二苯基乙二胺氢溴酸盐和二苯基乙二胺酒石酸盐的中和效果,发现以KOH调节水溶液至pH=12-14时水解产率最高。
3.以(R,R)-1,2-二苯基乙二胺和Tp为配体,合成了一种新的单氢钌配合物TpRu(PPh_3)(η~1-PhCHNH_2CHNH_2Ph)H结构经IR、EA、~1H NMR和(31)~PNMR确证。用该催化剂催化氢化前手性酮时,发现其对位阻较小的脂肪族酮的催化氢化作用较明显。但由于配体η~1-PhCHNH_2CHNH_2Ph上N-Cσ-键容易发生自由旋转,所以该化合物对前手性酮的氢化还原不具有不对称催化作用。
Hydrogenation of unsaturated compounds catalyzed by Ruthenium(Ⅱ) complexes with[Ru]-H bond has been widely investigated.The research emphasis focuses on how to desgin ligands to synthesize the reactive complexes.In this thesis,the main types of catalytic hydrogenation of olefins and synthesis of complexes of chiral diamines and chiral phosphorus ligands are reviewed.
The main work can be summarized as follows:
1.Hydrogenation of olefins catalyzed by TpRuH(PPh_3)(CH_3CN) [Tp=Hydrotris(pyrazoly1)borate]in anhydrous THF,H_2O/THF, CH_3CN/THF and ROH/THF(R=Me,Et,iso-propy1 and tert-buty1) has been studied,respectively.The remarkable promoting effect was found in the present of additives,such as H_2O,CH_3CN and ROH.A catalytic mechanism is proposed.The PPh_3 ligand in TpRuH(CH_3CN)L(L=H_2O,CH_3CN or ROH) is first replaced by the additive to reduce the steric hinderance,and then olefin replaces a ligand to form a complex TpRuH(olefin)L(L=H_2O, CH_3CN or ROH).The hydride ligand of TpRuH(olefin)L is transferred to the coordinated olefin and H2 is then coordinated to the formed vacant position to generate a complex withη~2-H_2 ligand.The metathesis reaction ofη~2-H_2 occurs,it transfers a hydrogen proton to the coordinated olefin to form a alkane,and regenerate an intermediate with Ru-H bond.Due to the steric hindrance of PPh3,it is difficult for olefin to react with TpRuH(PPh_3)(CH_3CN) in the absence of the additives,which is unfavorable for the catalytic hydrogenation.The turnover decreases with the increased steric hindrance of alcohols.
2.The synthetic techniques of diphenylethanediamine were studied. Effect of base as catalyst on the preparation of 2,4,5-triphenylimidazoline was studied and it was found that strong base is favorable for cyclization. Sodium isopropoxide is finally selected as the catalyst for this cyclization. Hydrolysis time of(±)-N-acety1-N'-benzoy1-1,2-ethylenediamine under the condition of 40%and 48%HBr was also studied.The optimizational hydrolysis concentration of HBr is 48%and hydrolytic time is 25h.Effect of pH value on the neutralization of diphenylethylenediamine hydrobromide and diphenylethylenediamine tartrate was studied.Using KOH to adjust the pH value of aqueous solution to 12-14 resulted in the highest yield.
3.A novel hydride complex TpRu(PPh_3)(η~1-PhCHNH_2CHNH_2Ph)H was synthesized using Tp and(R,R)-1,2-diphenylethanediamine as ligand, which was confirmed by IR spectroscopy,EA,~1H and ~(31)P NMR spectra. Althrough this complex was found to be reactive to catalytic hydrogenation of some ketones and esters,no chiral products were detected by ~1H NMR spectrum.Due to free rotation of the N-C -bond in the ligandη~1-PhCHNH_2CHNH_2Ph,this newly synthesized complex has no unsymetric catalytic reactivity to hydrogenation of prochiral ketones.
引文
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