CN106243132B - 一种金属Cu(I)配合物及其制备方法和应用 - Google Patents
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Abstract
本发明提供了一种金属Cu(I)配合物及其制备方法和应用。本发明是以三叔丁基膦亚胺负离子和N‑杂环卡宾为配体,与金属Cu(I)进行配位合成金属Cu(I)配合物,该类配合物能用来催化炔烃的硼氢化反应。本发明的特点在于:所用的金属Cu较便宜、配合物在烃类溶剂中具有较高的溶解性、催化反应所需反应条件温和、反应产率较高、具有专一的区域和立体选择性。该催化剂制备成本低、催化效率高,具有潜在的规模化应用前景。
Description
技术领域:
本发明涉及金属有机配合物,具体属于一种金属Cu(I)配合物及其制备方法,以及该配合物作为催化剂在炔烃硼氢化反应中的应用。
背景技术:
烯基硼试剂作为一种重要的有机中间体,能进一步发生形成C-C键、C-X键的反应,例如Suzuki-Miyaura交叉偶联反应、B(硼)-Heck型反应,而这些反应又可用于药物的合成。炔烃的硼氢化反应作为一种高效制备烯基硼试剂的方法受到广泛关注,该反应在过去主要以有毒贵金属催化为主,而在药物合成中有毒贵金属容易残留,会使药物产生毒副作用,因此发明一种高效、环境友好、条件温和的铜催化剂可以避免药物的毒副作用。本发明也是首次引入三叔丁基膦亚胺类有机小分子作为金属铜的配体,所得配合物可以用来高效、专一的催化炔烃的硼氢化反应。
发明内容:
本发明的目的在于提供一种金属Cu(I)配合物及其制备方法,该配合物毒性小、制备成本低,且可作为催化剂应用在催化炔烃的硼氢化反应中。
本发明提供的一种金属Cu(I)配合物,结构式为A或B:
式中tBu表示叔丁基。
本发明提供的一种金属Cu(I)配合物的制备方法,反应式为(1)或(2),式中tBu表示叔丁基:
制备方法,包括如下步骤:
1)在一个干燥玻璃瓶中将(NHC)CuCl溶于干燥的THF中形成悬浊液,然后将玻璃瓶放入手套箱冰箱中冷冻0.5-1.5小时;
2)在另一个干燥玻璃瓶中将0.95当量的[tBu3PN]Li溶于相同量干燥的THF中,然后将玻璃瓶放入手套箱冰箱中冷冻0.5-1.5小时;
3)将步骤1)和步骤2)中冷的(NHC)CuCl和冷的[tBu3PN]Li移出冰箱,在手套箱中将步骤2)中冷的[tBu3PN]Li溶液在搅拌下滴加到步骤1)中冷的(NHC)CuCl悬浊液中,滴加完毕后继续在手套箱中在室温下搅拌10-15小时;
4)反应完全后将溶剂THF在真空下挥发得油状物,然后加入一定量正戊烷或正己烷得一悬浊液,并在室温下搅拌几分钟,然后通过中性硅藻土短垫过滤除掉悬浊液中的不溶物,将滤液放入冰箱中冷冻5小时,再用中性硅藻土过滤,再冷冻滤液,重复几次得到清澈的正戊烷或正己烷溶液,将清澈溶液真空抽干溶剂后得到白色结晶固体,即配合物A或B。
上述步骤中NHC表示配体a或b。
本发明以三叔丁基膦亚胺负离子和N-杂环卡宾为配体,与金属Cu(I)进行配位合成金属Cu(I)配合物,该类配合物能用来催化炔烃的硼氢化反应。本发明的优点在于:所用的金属Cu较便宜、配合物在烃类溶剂中具有较高的溶解性、催化反应所需反应条件温和、反应产率较高、具有专一的区域和立体选择性。该催化剂制备成本低、催化效率高,具有潜在的规模化应用前景。
附图说明:
图1实施例1中配合物A的X-单晶衍射图;
图2为实施例1中配合物B的X-单晶衍射图;
图3为实施例1中配合物A的核磁氢谱图、碳谱图和磷谱图;
图4为实施例1中配合物B的核磁氢谱图、碳谱图和磷谱图;
图5为实施例1中配合物A催化苯乙炔的硼氢化反应13小时的氢谱图;
图6为实施例1中配合物B催化苯乙炔的硼氢化反应13小时的氢谱图;
图7为实施例1中配合物B催化苯乙炔的硼氢化反应0.5小时的氢谱图;
图8为实施例1中配合物A催化苯乙炔的硼氢化反应0.5小时的氢谱图;
图9为实施例2的氢谱图和碳谱图;
图10为实施例3的氢谱图和碳谱图;
图11为实施例4的氢谱图和碳谱图;
图12为实施例5的氢谱图和碳谱图;
图13为实施例6的氢谱图和碳谱图;
图14为实施例7的氢谱图和碳谱图;
图15为实施例8的氢谱图和碳谱图;
图16为实施例9的氢谱图和碳谱图;
图17为实施例10的氢谱图和碳谱图;
图18为实施例11的氢谱图和碳谱图;
图19为实施例12的氢谱图和碳谱图;
图20为实施例13的氢谱图和碳谱图;
图21为实施例14的氢谱图和碳谱图;
图22为实施例15的氢谱图和碳谱图;
图23为实施例16的氢谱图和碳谱图;
图24为实施例17的氢谱图和碳谱图;
图25为实施例18的氢谱图和碳谱图;
具体实施方式:
实施例1:金属Cu(I)配合物(催化剂)A和B的制备
1)在一个20ml干燥玻璃瓶中将0.2mmol(NHC)CuCl溶于3ml干燥的THF中形成悬浊液,然后将玻璃瓶放入手套箱冰箱中在-35℃下冷冻1h;
2)在另一个20ml干燥玻璃瓶中将42.3mg(0.95eq)[tBu3PN]Li溶于3ml干燥的THF中,然后将玻璃瓶放入手套箱冰箱中,在-35℃下冷冻1h;
3)将2)中冷的[tBu3PN]Li溶液在搅拌下缓慢滴加到1)中冷的(NHC)CuCl悬浊液中,滴加完毕后继续在手套箱中在室温下搅拌13h;
4)反应完全后将溶剂(THF)在真空下抽干得油状液渣,然后加入7ml正戊烷或正己烷得一悬浊液,并在室温下搅拌15min,然后通过中性硅藻土短垫过滤除掉不溶物,将滤液放入冰箱中在-35℃下冷却3-4h,再用中性硅藻土过滤,再冷冻滤液,重复几次得到清澈的正戊烷或正己烷溶液,将清澈溶液干燥后得到白色结晶固体,即配合物A或B。反应方程式表示如下:
式中a和b表示NHC(氮杂环卡宾配体)。
配合物A和B均可作为炔烃硼氢化反应的催化剂。在室温条件下,用5mol%催化剂A和催化剂B分别催化苯乙炔的硼氢化反应,当反应时间在13小时以上时,反应产率都在99%以上(见图5和图6);但是当反应时间控制在30分钟时,用催化剂B催化反应的转化率可以达到94%(见图7),而用催化剂A催化反应的转化率仅为82%(见图8)。可见催化剂B的催化效果要优于催化剂A,因此在以下实施例2-18中均以配合物B为催化剂。
实施例2~18均在手套箱中操作,将催化剂B(4.9mg,5mol%)加入到20mL的带有螺旋盖的反应瓶中,随后加入干燥的苯或甲苯(2mL)作为溶剂,将硼烷化合物HB(pin)(28mg,1.1eq.)慢慢加入到上述溶液中,最后加入炔烃反应物(0.2mmol,1eq.)。反应液在室温下搅拌5小时以上。待反应完全后,旋转蒸发除去溶剂得油状液体,用乙醚(3mL)浸洗3次,利用硅胶短柱进行过滤,合并滤液,溶剂再用真空泵除去得到产物纯品。(实施例2-18中所示产率均为分离产率)。
实施例2:用配合物B催化苯乙炔类化合物的硼氢化反应,得产物2a,产率89%。
实施例3:用配合物B催化对氯苯乙炔的硼氢化反应,得产物2b,产率99%。
实施例4:用配合物B催化邻氟苯乙炔的硼氢化反应,得产物2c,产率99%。
实施例5:用配合物B催化对甲基苯乙炔的硼氢化反应,得产物2d,产率98%。
实施例6:用配合物B催化对甲氧基苯乙炔的硼氢化反应,得产物2e,产率74%。
实施例7:用配合物B催化间甲基苯乙炔的硼氢化反应,得产物2f,产率87%。
实施例8:用配合物B催化对三氟甲基苯乙炔的硼氢化反应,得产物2g,产率81%。
实施例9:用配合物B催化苯丁炔的硼氢化反应,得产物2h,产率79%。
实施例10:用配合物B催化环己基乙炔的硼氢化反应,得产物2i,产率66%。
实施例11:用配合物B催化2-乙烯基-苯基炔丙基醚的硼氢化反应,得产物2j,产率86%。
实施例12:用配合物B催化间氟苯乙炔的硼氢化反应,得产物2k,产率77%。
实施例13:用配合物B催化5-氯-戊炔的硼氢化反应,得产物2l,产率61%。
实施例14:用配合物B催化3-【酰胺基】-丙炔的硼氢化反应,得产物2m,产率99%。
实施例15:用配合物B催化炔丙基苄基醚的硼氢化反应,得产物2n,产率76%。
实施例16:用配合物B催化碳酸叔丁醇炔丙醇酯的硼氢化反应,得产物2o,产率89%。
实施例17:用配合物B催化二炔丙基-对甲基苯磺胺的硼氢化反应,得产物2p,产率81%。
实施例18:用配合物B催化二苯乙炔的硼氢化反应,得产物2q,产率78%。
Claims (3)
1.一种金属Cu(I)配合物,其特征在于,结构式为A或B:
2.如权利要求1所述的一种金属Cu(I)配合物的制备方法,其特征在于,反应式为(1)或(2),式中tBu表示叔丁基:
3.如权利要求1所述的金属Cu(I)配合物作为催化剂在炔烃硼氢化反应中的应用。
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Mononuclear carbene dithiolate [Ni(NHX)(’S2C’)] complexes with HNX = HNPiPr3 coligands (‘S2C’2- = 1,3-imidazolidinyl-N,N’-bis(2-benzenethiolate)(2-));Frank W. et al.;《Z.Anorg.Allg.Chem.》;20011231;第627卷(第5期);第1034-1038页 * |
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