CN112705268A - 用于催化有氧氧化反应的两性离子-钌络合物 - Google Patents

用于催化有氧氧化反应的两性离子-钌络合物 Download PDF

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CN112705268A
CN112705268A CN202011159817.5A CN202011159817A CN112705268A CN 112705268 A CN112705268 A CN 112705268A CN 202011159817 A CN202011159817 A CN 202011159817A CN 112705268 A CN112705268 A CN 112705268A
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metal complex
zwitterionic ligand
zwitterionic
alcohol
amide
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CN112705268B (zh
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胡荣斌
林应邦
伍永轩
杨英洋
柯志海
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Chinese University of Hong Kong CUHK
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Abstract

提供了两性离子配体金属络合物和使用两性离子配体金属络合物的有氧氧化方法。两性离子配体金属络合物可以包括过渡金属盐和两性离子配体，所述两性离子配体可以包括非共轭酰胺阴离子‑鏻阳离子，酰胺阴离子‑铵阳离子或亚胺阳离子。有氧氧化的方法可以包括将两性离子配体金属络合物与可氧化的化合物和分子氧结合以实现从可氧化的化合物中分离出氧化的化合物。

Description

用于催化有氧氧化反应的两性离子-钌络合物
相关申请的交叉引用
本申请要求2019年10月25日提交的美国临时申请序列号62/925,943的权益，其公开内容通过引用以其全文并入本文，包括所有图、表和附图。
背景技术
催化是许多化学过程的核心要求。过渡金属催化的转化是催化的主要领域。配体对于决定催化性能(包括反应性、效率甚至选择性)至关重要。因此，配体的设计和制备是一个不断发展的研究领域。努力开发证明参数(诸如催化剂中心的空间和电子需求)易于调节的新型配体，这对于扩大范围和实现新反应至关重要。中性配体因其高度易获得性和稳定性而最常用。近年来，将带电荷的部分接枝到中性配体上已成为一种新的配体改性方法，可精细调节催化剂的性能并揭示新的反应性。例如，已使用带有与配体系统共轭的阳离子或阴离子部分的膦和N-杂环卡宾，以增强催化性能。
两性离子涉及同一分子中带正电荷和负电荷的配偶体的位点隔离，是某些反应中新兴的一类有机催化剂，表现出不同寻常的反应性和选择性。如果电荷对不通过电荷离域而自中和，则可以获得更强的阳离子和阴离子配偶体。然而，非共轭的两性离子不易制备，因此在过渡金属催化中它们作为配体的应用尚未得到充分利用。
最近，开发了基于亚胺阳离子/酰胺阴离子对的新型两性离子有机催化剂ZW1，如图1A所示(Lam et al.ACS Catal.2019，9，8083-8092)。ZW1易于通过氮丙啶1与4-吡咯烷二吡啶的反应一步制备，其中ZW1的刚性骨架可实现电荷的有效位点隔离。这类两性离子催化剂已成功应用于酯交换反应，如图1B所示。已发现，电荷对与两性离子ZW1中的吡咯烷鎓部分有协同作用，以通过非经典氢键(NCHB)相互作用激活酯的羰基，而碱性磺酰胺阴离子使醇去质子化。尚未开发出这种形成NCHB的能力以形成具有作为催化剂潜力的两性离子配体金属络合物。
发明内容
本发明的实施方式提供了两性离子配体金属络合物和使用两性离子配体金属络合物的有氧氧化方法。两性离子配体金属络合物可以包括过渡金属盐和两性离子配体。两性离子配体可以包括非共轭酰胺阴离子-鏻阳离子，酰胺阴离子-铵阳离子或亚胺阳离子。有氧氧化的方法可以包括将两性离子配体金属络合物与可氧化的化合物和分子氧结合以实现从可氧化的化合物中分离出氧化的化合物。分离的氧化的化合物可以是，例如，醛或酮，但是实施方式并不限于此。
在一个实施方式中，两性离子配体金属络合物可以包括过渡金属盐和两性离子配体，所述两性离子配体包括非共轭酰胺阴离子-鏻阳离子，酰胺阴离子-铵阳离子或亚胺阳离子。酰胺阴离子可以是但不限于磺酸酰胺，所述磺酸酰胺可以是但不限于甲苯磺酸酰胺阴离子。亚胺阳离子可以是但不限于4-吡咯烷二吡啶的亚胺。鏻阳离子可以是但不限于三烷基膦的鏻离子。包括非共轭酰胺阴离子-鏻阳离子或酰胺阴离子-铵或亚胺阳离子的两性离子配体可以是应变环酰胺的开环产物，例如但不限于氮丙啶酰胺。氮丙啶酰胺可以是但不限于环己烯亚胺。金属盐可以是但不限于钌(III)盐，例如但不限于RuCl3。
在另一个实施方式中，使用两性离子配体金属络合物进行有氧氧化的方法可以包括将两性离子配体金属络合物与可氧化的化合物和分子氧结合以实现从可氧化的化合物中分离出氧化的化合物，所述氧化的化合物例如是但不限于醛或酮。可氧化的化合物是伯醇、仲醇、对苯二酚、二氢吲哚或1，2，3，4-四氢喹喔啉。这些伯醇和仲醇包括脂肪醇、苄醇、烯丙醇、二苯甲醇、1-苯基烯丙醇或1-烯基-烯丙醇。这些伯醇或仲醇中的任何一个均可在醇的除带有醇官能度的碳之外的任何部分上被非需氧的可氧化取代基取代。在一些情况下，伯醇或仲醇可以包括可氧化成双氧化的第二醇(含产物)，或根据温度和分子氧的化学计量，实现形成单氧化的醇(含化合物)。分子氧可以从空气中提供。可以使用溶剂(例如，1，2-二氯乙烷(DCE))，并且可以将反应混合物加热到高于环境温度的温度，最高达到或超过100℃(例如，在23℃至100℃范围或40℃至100℃范围中)。
附图说明
图1A显示了根据本发明实施方式的形成两性离子配体ZW1和ZW2的反应方案。
图1B显示了使用ZW1作为催化剂进行酯交换反应的反应方案。
图1C显示了ZW2的硝酸质子化形成的反应方案以及质子化物质ZW2-HNO3的X线结构。
图2显示了根据本发明的实施方式的用于与ZW2形成金属络合物的反应方案。
图3A显示了使用氯化钌(III)配体催化剂对对甲氧基苄醇进行有氧氧化的反应方案。
图3B显示了用RuCl3·3H2O和以下所示的各种配体对图3A进行氧化的产率和选择性的条形图。
图4A显示了根据本发明的实施方式，使用Ru(III)-ZW2催化剂对伯醇和仲醇进行有氧氧化的反应方案。
图4B显示了根据本发明的实施方式，用于将图4A所示的伯醇有氧氧化为各种苄基醛和脂族醛的醛的结构。
图4C显示了根据本发明的实施方式，用于分别如图4A所示将仲醇和烯丙醇有氧氧化成各种苄基酮和脂肪酮以及α，β-不饱和醛的酮和醛的结构。
图5A是根据本发明的实施方式，使用Ru(III)-ZW2催化剂将1，4-氢醌有氧氧化为1，4-苯醌的反应方案。
图5B是根据本发明的实施方式，使用Ru(III)-ZW2催化剂将二氢吲哚有氧氧化为吲哚的反应方案。
图5C是根据本发明的实施方式，使用Ru(III)-ZW2催化剂将1，2，3，4-四氢喹喔啉有氧氧化为喹喔啉的反应方案。
图6显示了根据本发明的实施方式，使用Ru(III)-ZW2催化剂，以空气为氧源对对甲氧基苄醇进行有氧氧化的反应方案，以及苄醇对脂肪醇上的氧化选择性。
图7是立体选择性转移半氢化反应的反应方案。
具体实施方式
本发明的实施方式提供了两性离子配体金属络合物和使用两性离子配体金属络合物的有氧氧化方法。两性离子配体金属络合物可以包括过渡金属盐和两性离子配体，所述两性离子配体可以包括非共轭酰胺阴离子-鏻阳离子，酰胺阴离子-铵阳离子或亚胺阳离子。有氧氧化的方法可以包括将两性离子配体金属络合物与可氧化的化合物和分子氧结合以实现从可氧化的化合物中分离出氧化的化合物。分离的氧化的化合物可以是，例如，醛或酮，但是实施方式并不限于此。
如图1A所示，除了吡啶鎓配体ZW1之外，根据本发明实施方式的鏻两性离子配体ZW2可以通过使三正丁基膦与氮丙啶1反应进行制备。ZW2具有空气/水分稳定性，其制备容易扩展。与ZW1中的非经典氢键(NCHB)相似，硝酸根阴离子与HNO3和ZW2之间形成的盐ZW2-HNO3中的鏻阳离子部分相互作用，其中，通过X线晶体学表征形成NCHB，如图1C所示。在一个实施方式中，两性离子配体(例如但不限于ZW2)能够与一种或多种过渡金属盐M-X形成络合物以形成电荷中性金属络合物，诸如ZW2-M，如图2所示。该络合物显示出与金属中心配位的酰胺阴离子，通过NCHB的形成使鏻阳离子部分与抗衡阴离子X从金属中心解离，如图2所示。碱性抗衡阴离子X的解离可增强金属中心的反应性。根据本发明的实施方式，未采用其中银盐不可逆地除去金属的抗衡阴离子的通用方法，而是抗衡阴离子X保留在假定的两性离子-金属络合物ZW2-M中，紧邻金属中心。因此，酰胺和鏻/X部分被定位以协同形成双官能配体，而抗衡阴离子X可逆地配位至金属中心并从金属中心解离。这种半稳定的相互作用使配体能够改变结合模式并沿反应路径稳定反应性中间体，从而增强各种反应的催化性能。
为了证明这种行为，可以将醇氧化为羰基，如图3A所示。转化是研究和工业中普遍存在的关键反应，对于形成羰基化合物(如药物、农药和香料)很重要。可以使用1个大气压(atm)的分子氧作为氧化剂，由于水是唯一的副产物，因此在工业工艺中非常需要使用该氧化剂。已经使用各种定制的过渡金属络合物研究了这种类型的反应。当在没有外部配体的情况下进行时，除非使用高压和高温，否则在室温下使用三氯化钌作为催化剂将醇2a氧化为醛3a的反应缓慢。如图3B所示，主要形成醚副产物4a。相反，根据本发明的实施方式，当添加两性离子ZW1作为外部配体时，氧化平稳地进行。当鏻两性离子ZW2在其他相同条件下用作配体时，性能进一步增强，以97％的产率得到所需的醛3a，而未形成醚副产物4a。配体与Ru的比例为3∶1(配体：Ru)可提供最佳的催化活性。与许多其他常见的电荷中性配体(诸如膦PL1-PL4、胺NL1-NL4和N-杂环卡宾IPr)相比，使用两性离子配体ZW2的催化性能要优越得多。注意ZW2的HCl盐进行反应，但是反应缓慢，表明碱性酰胺阴离子在与金属中心配位的催化氧化反应中很重要。ZW2的分段催化剂盐PBr和甲苯磺酰胺NLi可单独进行缓慢反应，或将这些组分以1∶1的混合物形式用作配体时，反应缓慢，这表明ZW2位点分离的鏻和酰胺部分对形成活性Ru催化剂具有协同作用。
如图4A所示，两性离子钌络合物的催化性能容易氧化广泛范围的醇底物。带有给电子(甲基、甲氧基和二甲胺)或吸电子(氯、溴、碘、硝基、甲基酯、三氟甲基和磺酰胺)取代基的苄醇可成功氧化成相应的醛(3a-3i)，如图4B所示。具有萘基、吡啶基和呋喃基取代基的醇与催化方案(3j-31)相容。如图4B所示，脂肪族伯醇可平稳地产生所需的醛(3m-3p)。值得注意的是，在温和的氧化反应条件下，底物3m中的烯烃官能团保持完整。
如图4C所示，多种仲醇3q-3z产生所需的芳基和烷基取代的酮3q-3z。可以升高反应温度以补偿仲醇底物固有的较慢反应。两性离子配体金属络合物催化性与烯丙醇3aa-3ad的氧化相容，得到相应的α，β-不饱和羰基化合物3aa-3ad。
参见图5A，在实施方式中，使用2.5mol％的Ru催化剂络合物，对苯二酚5a可以进行氧化脱氢以86％的产率产生1，4-苯醌6a。取代的对苯二酚5b-5d以优异的产率转化为1，4-苯醌6b-6d，而1，4-萘醌6e由1，4-二羟基萘5e形成。在本发明的另一个实施方式中，如图5B所示，二氢吲哚7到二氢吲哚8的氧化脱氢很容易进行。如图5C所示，还可以通过1，2，3，4-四氢喹喔啉9的双重氧化获得喹喔啉10。
氧化的实用性可以通过在环境空气中以克为单位进行反应来证明，如图6所示。升高温度以补偿由于分子氧浓度较低而降低的反应速率。在最佳条件下，2a的氧化反应平稳进行，以95％的产率得到醛。另外，可以简单地通过沉淀回收催化剂络合物，并且再循环的催化剂促进相同的反应，而没有观察到催化性能的损失。该催化方案还可以用于二醇2af的化学选择性氧化，并且仅获得单氧化产物3af。
图7是立体选择性转移半氢化反应的反应方案。参见图7，使用Ru(II)(低价金属以稳定氢化物)与ZW2配体一起可有效地催化二苯乙炔(11)的转移半氢化成反式1，2-二苯乙烯(12)，产率至少为80％。甚至更有利地，可以获得并观察到优异的立体选择性(12∶13＝40∶1)。相反，配体诸如三苯基膦和NHC卡宾IPr仅得到中等产率和立体选择性。
材料和方法
图4A-C的有氧氧化反应在指示的时间和温度下，在O2(1atm)下于密封管(容量为10mL)中，用DCE(1.5mL)中的2(0.3mmol)、RuCl3·3H2O(5mol％)、ZW2(15mol％)进行，并按产品结构提供单独的产率。
图5A-C的有氧氧化反应在O2(1atm)下于密封管(容量为10mL)中，用DCE(1.5mL)中的底物(0.3mmol)、RuCl3·3H2O(n mol％)、ZW2(3×n mol％)进行，并按产品结构提供单独的产率。
应该理解的是，本文描述的实施例和实施方式仅用于示例性目的，基于其的各种修改或改变能够被本领域技术人员领悟到，且其各种修改或改变应包括在本申请的精神和范围以及所附权利要求的范围内。另外，本文公开的任何发明或其实施方式的任何要素或限制可以与本文公开的任何和/或所有其他要素或限制(单独地或以任何组合)或任何其他发明或其实施方式组合，并且，所有这些组合是通过本发明的范围预期到的，但不对本发明的范围构成限制。

Claims (20)

1.一种两性离子配体金属络合物，包括：
过渡金属盐；和
两性离子配体，
其中，所述两性离子配体包括非共轭酰胺阴离子-鏻阳离子或酰胺阴离子-亚胺阳离子。
2.根据权利要求1所述的两性离子配体金属络合物，其中，所述酰胺阴离子是磺酸酰胺阴离子。
3.根据权利要求2所述的两性离子配体金属络合物，其中，所述磺酰胺阴离子是甲苯磺酸酰胺阴离子。
4.根据权利要求1所述的两性离子配体金属络合物，其中，所述亚胺阳离子是4-吡咯烷二吡啶的亚胺。
5.根据权利要求1所述的两性离子配体金属络合物，其中，所述阳离子是三烷基膦的鏻离子。
6.根据权利要求1所述的两性离子配体金属络合物，其中，所述两性离子配体是应变环酰胺的开环产物。
7.根据权利要求6所述的两性离子配体金属络合物，其中，所述应变环酰胺是氮丙啶酰胺。
8.根据权利要求7所述的两性离子配体金属络合物，其中，所述氮丙啶酰胺是环己烯亚胺。
9.根据权利要求6所述的两性离子配体金属络合物，其中，所述应变环酰胺是磺酸酰胺。
10.根据权利要求9所述的两性离子配体金属络合物，其中，所述磺酸酰胺是芳香族磺酸酰胺。
11.根据权利要求10所述的两性离子配体金属络合物，其中，所述芳香族磺酸酰胺是甲苯磺酸酰胺。
12.根据权利要求1所述的两性离子配体金属络合物，其中，所述金属盐是钌(III)盐。
13.根据权利要求12所述的两性离子配体金属络合物，其中，所述钌(III)盐是RuCl3。
14.一种有氧氧化的方法，所述方法包括：
提供根据权利要求1的两性离子配体金属络合物；
提供可氧化的化合物；
提供分子氧；
将所述两性离子配体金属络合物、所述可氧化的化合物和所述分子氧结合以产生氧化的化合物；和
从所述可氧化的化合物中分离出所述氧化的化合物。
15.根据权利要求14所述的方法，其中，所述两性离子配体金属络合物的两性离子配体是2-甲苯磺酰基环己基-三丁基鏻。
16.根据权利要求14所述的方法，其中，金属盐两性离子配体金属络合物是氯化钌(III)的三水合物。
17.根据权利要求14所述的方法，其中，所述可氧化的化合物是伯醇、仲醇、对苯二酚、二氢吲哚或1，2，3，4-四氢喹喔啉，
其中，所述伯醇是脂肪醇、苄醇或烯丙醇，
其中，所述仲醇是脂肪醇、苄醇、烯丙醇、二苯甲醇、1-苯基烯丙醇或1-烯基烯丙醇，和
其中，所述氧化的化合物是醛或酮。
18.根据权利要求14所述的方法，所述方法进一步包括：
提供溶剂；和
将所述溶剂与所述两性离子配体金属络合物、所述可氧化的化合物和所述分子氧混合。
19.根据权利要求18所述的方法，其中，所述溶剂是1，2-二氯乙烷(DCE)，并且
其中，提供分子氧包括提供空气。
20.根据权利要求14所述的方法，所述方法进一步包括加热至在23℃至100℃范围中的一个温度。
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