CN114539327B - 一种手性三齿亚胺P,N,N-配体和制备方法及在Cu-催化不对称炔丙基转化中的应用 - Google Patents

一种手性三齿亚胺P,N,N-配体和制备方法及在Cu-催化不对称炔丙基转化中的应用 Download PDF

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CN114539327B
CN114539327B CN202011346896.0A CN202011346896A CN114539327B CN 114539327 B CN114539327 B CN 114539327B CN 202011346896 A CN202011346896 A CN 202011346896A CN 114539327 B CN114539327 B CN 114539327B
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胡向平
万银波
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明提供一种手性三齿亚胺P,N,N‑配体和制备方法及在Cu‑催化不对称炔丙基转化中的应用，该手性三齿亚胺P,N,N‑配体性质稳定、对空气和湿度具有很好忍耐力的内含N‑H官能团，其以手性二茂铁膦‑1,2‑二苯基乙二胺化合物与2‑酰基吡啶化合物为原料，在脱水剂作用下，在温和条件下一步反应制备。该新型手性三齿亚胺P,N,N‑配体与Cu金属前体组成的催化剂在不对称炔丙基转化反应中具有优异的催化活性和立体选择性。

Description

一种手性三齿亚胺P,N,N-配体和制备方法及在Cu-催化不对 称炔丙基转化中的应用
技术领域
本发明涉及有机合成领域，具体涉及一种应用于Cu-催化不对称炔丙基转化反应的内含N-H官能团的新型手性三齿亚胺P,N,N-配体及其制备方法和应用。
背景技术
Cu-催化的不对称炔丙基转化反应在过去的十多年里蓬勃发展，成为构建含炔基手性化合物及手性环状骨架重要和高效的方法之一[(a)Ljungdahl,N.；Kann,N.Transition-Metal-Catalyzed Propargylic Substitution.Angew.Chem.,Int.Ed.2009,48,642-644.(b)Miyake,Y.；Uemura,S.；Nishibayashi,Y.CatalyticPropargylic Substitution Reactions.ChemCatChem 2009,1,342-356.(c)Ding,C.-H.；Hou,X.-L.Catalytic Asymmetric Propargylation.Chem.Rev.2011,111,1914-1937.(d)Hu,X.-H.；Liu,Z.-T.；Shao,L.；Hu,X.-P.Recent Advances in CatalyticStereocontrolled Cycloaddition with Terminal Propargylic Compounds.Synthesis2015,913-923.(e)Zhang,D.-Y.；Hu,X.-P.Recent Advances in Copper-CatalyzedPropargylic Substitution.Tetrahedron Lett.2015,56,283-295.(f)Sakata,K.；Nishibayashi,Y.Mechanism and Reactivity ofCatalytic Propargylic SubstitutionReactions via Metal–allenylidene Intermediates:A Theoretical Perspective.Catal.Sci.Technol.2018,8,12-25.(g)Roh,S.W.；Choi,K.；Lee.C.Transition MetalVinylidene-and Allenylidene-Mediated Catalysis in OrganicSynthesis.Chem.Rev.2019,119,4293-4356.]。目前，适用于Cu-催化的不对称炔丙基转化反应的手性配体包括三类：1)手性联萘或联苯骨架的双膦配体如BINAP、Cl-MeO-BIPHEP等；2)手性吡啶双噁唑啉配体；3)由我们自主发展的手性三齿P,N,N-配体[(h)Zhang,C.；Hu,X.-H.；Wang,Y.-H.；Zheng,Z.；Xu,J.；Hu,X.-P.Highly Diastereo-and EnantioselectiveCu-Catalyzed[3+3]Cycloaddition ofPropargyl Esters with Cyclic Enamines towardChiral Bicyclo[n.3.1]Frameworks.J.Am.Chem.Soc.2012,134,9585-9588；(i)Zhu,F.-L.；Zou,Y.；Zhang,D.-Y.；Wang,Y.-H.；Hu,X.-H.；Chen,S.；Xu,J.Hu,X.-P.Enantioselective Copper-Catalyzed Decarboxylative Propargylic Alkylation ofPropargyl β-Ketoesters with a Chiral Ketimine P,N,N-Ligand.Angew.Chem.,Int.Ed.2014,53,1410-1414.]。因此目前适用于Cu-催化不对称炔丙基转化反应的手性配体还十分有限，许多Cu-催化不对称炔丙基转化反应还未能取得令人满意的研究结果，发展新型高效的手性配体仍是Cu-催化不对称炔丙基转化反应研究的核心。
发明内容
本发明的目的是提供一种含有N-H官能团的新型手性三齿亚胺P,N,N-配体，N-H官能团的存在有利于配体与底物间的次级效应，从而实现高效的Cu-催化不对称炔丙基转化反应。
具体地，本发明所述新型手性三齿亚胺P,N,N-配体具有式I所示结构；
其中，Ar为苯基或取代苯基、萘基或取代萘基、杂环芳香基团或取代杂环芳香基团；所述取代苯基、取代萘基、取代杂环芳香基团的取代基选自C1-C40烷基、C1-C40烷氧基、卤素、硝基、酯基或氰基中的一种或多种；所述杂环芳香基团是指含一种或多种N、O、S等杂原子的五元或六元芳香基团；
R选自氢、C1-C40烷基、C3-C12环烷基、苯基及取代苯基、苄基和取代苄基等；所述苯基以及苄基的取代基各自独立地选自C1-C40烷基、C1-C40烷氧基、卤素、硝基、酯基或氰基中的一种或多种；
为实现上述目的，在本发明中，所述手性三齿P,N,N-亚胺配体I的制备方法按以下反应路线进行，
在本发明中，所述手性三齿亚胺P,N,N-配体I的制备方法包括以下步骤：
氮气保护下，将手性二茂铁膦-1,2-二苯基乙二胺化合物II、2-酰基吡啶化合物III与脱水剂加入反应介质中回流搅拌3-24小时，反应完毕后减压浓缩至基本无溶剂，硅胶柱层析分离，减压浓缩，真空干燥制备手性三齿P,N,N-亚胺配体。
在本发明的实施方式中，所述脱水剂选自无水Na2SO4、无水MgSO4、无水K2CO3、TiCl4、活性Al2O3等中的一种或多种。优选为无水Na2SO4、活性Al2O3。
在本发明中，所述反应介质选自质子性溶剂和/或非质子性溶剂。包括甲醇、乙醇、四氢呋喃、甲苯、乙腈和二氯甲烷中的一种或多种；优选为甲苯。(上述反应介质均为无水介质)。
在本发明的实施方式中，所述手性二茂铁膦-1,2-二苯基乙二胺化合物与2-酰基吡啶化合物的摩尔比1:1-10，优选为1:1。
在本发明的实施方式中，所述手性二茂铁膦-1,2-二苯基乙二胺化合物与脱水剂的摩尔比1:1-10，优选为1:2。
在本发明中，所述手性三齿亚胺P,N,N-配体I，其优势配体结构如下：
本发明还涉及上述配体在Cu-催化不对称炔丙基转化反应中的应用。
本发明提供的手性三齿亚胺P,N,N-配体，其可用于Cu-催化不对称炔丙基转化反应中，将手性三齿亚胺P,N,N-配体与Cu金属催化剂前体按摩尔比1.1：1组成催化剂，反应底物与催化剂的比例为0.05：1，反应时间为24小时。
其中，所述铜金属催化剂前体为铜盐，选自无水CuCl、CuI、Cu(CH3CN)4PF6、Cu(CH3CN)4BF4、CuCl2、Cu(OAc)2、Cu(OTf)2中的一种或多种。
本发明的有益效果：
本发明所述新型手性三齿亚胺P,N,N-配体，内含有N-H官能团，有利于配体与底物间的次级效应，从而实现传统Cu-催化不对称炔丙基转化未能实现的反应。本发明手性三齿亚胺P,N,N-配体还具有制备方法简单，性质稳定、对空气和湿度具有很好的忍耐力，结构易修饰等特点。
附图说明
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。以下，结合附图来详细说明本发明的实施方案，其中：
图1为实施例1制备的手性三齿P,N,N-亚胺配体(Rc,Sp,Sc,Sc)-I-1氢谱；
图2为实施例1制备的手性三齿P,N,N-亚胺配体(Rc,Sp,Sc,Sc)-I-1磷谱；
图3为实施例8制备的1-羟基-4-(1-苯基丙-2-炔-1-基)-2-萘甲酸甲酯氢谱；
图4为实施例8制备的1-羟基-4-(1-苯基丙-2-炔-1-基)-2-萘甲酸甲酯碳谱；
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件或按照制造厂商所建议的条件。
除非另行定义，文中所使用的所有专业与科学用语与本领域熟练人员所熟悉的意义相同。本发明所使用的试剂或原料均可通过常规途径购买获得，如无特殊说明，本发明所使用的试剂或原料均按照本领域常规方式使用或者按照产品说明书使用。此外，任何与所记载内容相似或均等的方法及材料皆可应用于本发明方法中。文中所述的较佳实施方法与材料仅作示范之用。本发明实施例的核磁共振是通过Bruker 400核磁共振仪测定。
实施例1由手性二茂铁膦-1,2-二苯基乙二胺化合物(Rc,Sp,Sc,Sc)-II-1与2-吡啶甲醛III-1为原料制备手性三齿P,N,N-亚胺配体(Rc,Sp,Sc,Sc)-I-1。
氮气保护下，在反应瓶中加入手性二茂铁膦-1,2-二苯基乙二胺化合物(Rc,Sp,Sc,Sc)-II-1(1.0mmol，1.0equiv)、2-吡啶甲醛III-1(1.0mmol，1.0equiv)和无水Na2SO4(2.0mmol，2.0equiv)，加入5.0mL无水甲苯，回流搅拌反应24h。反应完毕，减压浓缩至基本无溶剂，硅胶柱层析分离，减压浓缩，真空干燥得黄色固体，81％收率。
手性三齿P,N,N-亚胺配体(Rc,Sp,Sc,Sc)-I-1的核磁共振氢谱和磷谱如图1、图2所示：1H NMR(400MHz,CDCl3)δ8.54–6.68(m,24H),5.2(s,1H),4.53–4.51(m,1H),4.35(t,J＝2.6Hz,1H),4.33–4.29(m,1H),4.10–4.06(m,2H),3.96(d,J＝8.4Hz,1H),3.78–3.69(m,6H),1.47(t,J＝6.8Hz,3H).31P NMR(162MHz,CDCl3):δ-25.5.HRMS cal.for C44H41FeN3P+[M+H]+:698.2382,found:698.2384.
实施例2乙醇作为反应溶剂制备(Rc,Sp,Sc,Sc)-I-1
将实施例1中的溶剂甲苯用乙醇代替，其余同实施例1。反应得到(Rc,Sp,Sc,Sc)-I-1，74％收率。
实施例3甲醇作为反应溶剂制备(Rc,Sp,Sc,Sc)-I-1
将实施例1中的溶剂甲苯用甲醇代替，其余同实施例1。反应得到(Rc,Sp,Sc,Sc)-I-1，42％收率。
实施例4无水MgSO4为脱水剂制备(Rc,Sp,Sc,Sc)-I-1
将实施例1中无水Na2SO4用无水MgSO4代替，其余同实施例1。得到(Rc,Sp,Sc,Sc)-I-1，65％收率。
实施例5无水K2CO3为脱水剂制备(Rc,Sp,Sc,Sc)-I-1
将实施例1中的无水Na2SO4替换为无水K2CO3，其余同实施例1。得到(Rc,Sp,Sc,Sc)-I-1，26％收率。
实施例6无水Al2O3为脱水剂制备(Rc,Sp,Sc,Sc)-I-1
将实施例1中的无水Na2SO4替换为无水Al2O3，其余同实施例1。得到(Rc,Sp,Sc,Sc)-I-1，76％收率。
实施例7无水Na2SO4用量提高1倍制备(Rc,Sp,Sc,Sc)-I-1
将实施例1中的无水Na2SO4用量提高到2mmol，其余同实施例1。得到(Rc,Sp,Sc,Sc)-I-1，67％收率。
实施例8(Rc,Sp,Sc,Sc)-I-1为配体，Cu(OAc)2为金属前体催化1-羟基-2-萘甲酸甲酯的炔丙基取代反应
氮气保护下，将Cu(OAc)2(0.015mmol,5.0mol％)，(Rc,Sp,Sc,Sc)-I-1(0.0165mmol,5.5mol％)溶于甲醇(1.0mL)中，室温(25℃)下搅拌1小时，加入1-羟基-2-萘甲酸甲酯S-1(0.3mmol)与1-苯基-2-丙炔基乙酸酯S-2(0.36mmol)、Et3N(0.36mmol)、甲醇(2.0mL)，将其置于室温下继续反应24小时。除去溶剂后，硅胶柱分离得到产物1-羟基-4-(1-苯基丙-2-炔-1-基)-2-萘甲酸甲酯，产率为82％，91％ee的对映选择性。
1-羟基-4-(1-苯基丙-2-炔-1-基)-2-萘甲酸甲酯核磁共振氢谱和碳谱如图3、图4所示：1H NMR(400MHz,CDCl3)δ12.0(s,1H),8.48–7.22(m,10H),5.56(d,J＝2.8Hz,1H),3.99(s,1H),2.55(d,J＝2.4Hz,1H).13C NMR(100MHz,CDCl3)δ171.4,160.8,140.3,134.6,129.6,128.7,127.7,127.1,126.6,125.7,125.5,124.8,124.6,124.2,105.0,84.4,73.7,52.4,39.9.HRMS cal.for C21H17O3 +[M+H]+:317.1172,found:317.1172.
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (8)

1.一种手性三齿亚胺P,N,N-配体，其特征在于，该手性三齿亚胺P,N,N-配体内含N-H官能团，具有式I所示结构：
其中，Ar为苯基；R为氢。
2.一种如权利要求1所述手性三齿亚胺P,N,N-配体的制备方法，其特征在于，具体步骤：
氮气保护下，将手性二茂铁膦-1,2-二苯基乙二胺化合物II、2-酰基吡啶化合物III与脱水剂加入反应介质中回流搅拌6-24小时，反应完毕后减压浓缩至无溶剂，硅胶柱层析分离，减压浓缩，真空干燥制备手性三齿亚胺P,N,N-配体。
3.根据权利要求2所述的手性三齿亚胺P,N,N-配体的制备方法，其特征在于，所述反应介质选自质子性溶剂和/或非质子性溶剂。
4.根据权利要求2所述的手性三齿亚胺P,N,N-配体的制备方法，其特征在于，所述脱水剂选自无水Na2SO4、无水MgSO4、无水K2CO3、TiCl4、活性Al2O3中的一种或多种。
5.根据权利要求2所述的手性三齿亚胺P,N,N-配体的制备方法，其特征在于，所述手性二茂铁膦-1,2-二苯基乙二胺化合物与2-酰基吡啶化合物的摩尔比1：0.1-10。
6.根据权利要求2所述的手性三齿亚胺P,N,N-配体的制备方法，其特征在于，所述手性二茂铁膦-1,2-二苯基乙二胺化合物与脱水剂的摩尔比1：1-10。
7.一种如权利要求1所述的手性三齿亚胺P,N,N-配体在Cu-催化不对称炔丙基转化中的应用，其特征在于，所述手性三齿亚胺P,N,N-配体与铜金属前体组成的催化剂应用于不对称炔丙基转化反应中。
8.根据权利要求7所述的应用，其特征在于，将手性三齿亚胺P,N,N-配体与Cu金属催化剂前体按摩尔比1.1：1组成催化剂，反应底物与催化剂的比例为0.05：1，反应时间为24小时。
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