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CN101198581B - 使羧酸与碳亲电子试剂脱羧形成c-c键的方法 - Google Patents

使羧酸与碳亲电子试剂脱羧形成c-c键的方法 Download PDF

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CN101198581B
CN101198581B CN200680021005.6A CN200680021005A CN101198581B CN 101198581 B CN101198581 B CN 101198581B CN 200680021005 A CN200680021005 A CN 200680021005A CN 101198581 B CN101198581 B CN 101198581B
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L·古森斯
邓国军
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Abstract

本发明涉及通过羧酸盐与碳亲电子试剂在过渡金属化合物作为催化剂的存在下反应脱羧形成C-C键的方法。该方法是羧酸盐与碳亲电子试剂的脱羧交叉偶联反应，其中所述的催化剂系统包含两种过渡金属或过渡金属化合物，其中一种金属优选以彼此相差一价的氧化态存在，从而催化自由基脱羧反应，而第二种优选采取彼此相差两价的氧化态，从而催化交叉偶联反应的双电子过程。

Description

使羧酸与碳亲电子试剂脱羧形成C-C键的方法
本发明涉及经羧酸盐脱羧形成的碳亲核试剂与碳亲电子试剂在过渡金属催化剂存在下形成C-C键的方法。
联芳-亚结构是功能性材料、药物和作物保护制剂中的关键官能团。为了合成这样的化合物，尤其是使用芳基卤与硼酸的苏楚基偶联反应，因为其可以简单并以出色的产率来进行，并容许很多官能团和取代模式。特别令人感兴趣的是制备杀菌剂啶酰菌胺(Boscalid)的中间体化合物2-硝基-4’-氯联苯。在示意图1中作为苏楚基偶联反应的例子描述了其工业制备。
示意图1.苏楚基偶联反应
然而，尤其是对于工业应用，由于硼酸难以得到并因此导致高价格，所述的方法具有严重的缺点。其通过将乙烯基卤和芳基卤金属化并随后与三烷基硼酸酯反应来合成的成本过高并不易与所有的官能团共存。更广泛适用的是有机卤化物与二硼化合物的催化交叉偶联反应，但是由于所述的化合物价格高，而发现很难工业应用。由频哪醇或邻苯二氧硼烷制备硼酸由于成本高而在工业上很少有吸引力。
其它联芳合成在产率、可行性和应用领域方面通常明显不如苏楚基偶联反应。例如，由两种芳香烃在路易斯酸和质子酸的存在下相互反应的肖尔反应通常只提供不令人满意的产率并只能与少数官能团共存。冈伯格-巴克曼反应同样如此。更广泛适用的是两种芳基碘化物在铜化合物存在下相互偶联的乌尔曼反应，然而只有合成对称化合物时才实现较满意的产率。
与芳基镁、芳基锌或芳基锂的催化交叉偶联反应由于这些化合物难以操作和其与官能团的低相容性而没有苏楚基偶联反应有利。只有芳基硅氧烷和有毒的芳基锡烷表现出与芳基硼酸同样好的特性，然而在制备这些化合物时也产生了同样的问题。
这样就存在对始于以良好的可用性和可操作性以及低价格著称的碳亲核试剂的新交叉偶联反应的需要。羧酸的金属盐可广泛获得并因此是理想的起始原料。因此通过羧酸盐脱羧原位制备有机金属类并与碳亲电子试剂偶联的偶联反应令人很感兴趣，尤其是当它们也可以用于制备联芳时。
至今只有一个相关反应的例子，其中在作为络合的反应混合物组分的芳基卤过量存在下，羧酸铜热解时也形成尤其是相应的联芳。然而过高的温度(240℃)、低产率、大量铜盐和受限制的底物范围使所述的反应不适合于商业使用。
本发明的目的为，开发碳亲核试剂与碳亲电子试剂交叉偶联的通常适用的催化方法，其中通过金属羧酸盐脱羧原位形成碳亲核试剂。特别困难的是找到适合的催化剂系统，因为羧酸通常经自由基机理进行脱羧，而交叉偶联催化剂起作用的原因在于它们只选择性地促进双电子过程而抑制自由基反应步骤。
本发明的主题为通过羧酸盐与碳亲电子试剂在过渡金属或过渡金属化合物作为催化剂存在下脱羧形成C-C键的方法。
示意图2.本发明的羧酸盐与碳亲电子试剂的脱羧交叉偶联反应
令人惊讶地发现，包含两种或多种金属化合物的催化剂系统可以非常有效地催化根据示意图2的羧酸盐与碳亲电子试剂的脱羧交叉偶联反应。
优选催化剂系统包含两种不同的过渡金属化合物。其中第一种过渡金属可以采取氧化态相差一价而第二种氧化态彼此相差两价这样的系统特别适合。假设第一种过渡金属催化自由基脱羧反应，而第二种催化交叉偶联反应的双电子过程。令人惊讶地，这些同时进行的催化过程不相互干扰，很可能催化剂成分在它们的效应方面彼此增强，从而使脱羧步骤也在极低的催化剂量时已经于空前低的温度下进行了。
如果使用两种或多种不同的过渡金属或过渡金属化合物，则根据使用的底物作为第一种催化剂成分的第一种金属化合物可以化学计量量使用而作为第二种催化剂成分的第二种金属或金属化合物以催化量使用。
此外发现一种方法，其中使用这种催化剂系统，特征为通过挤出二氧化碳将羧酸盐转化为碳亲核试剂并与碳亲电子试剂而连接形成C-C键。
与所述的现有技术相比有利的是，羧酸盐比金属有机化合物如硼酸便宜得多、更容易获得且更易于操作。新催化剂与Nilsson所述的相比的优点在于，加入专门催化交叉偶联反应的第二种金属成分而形成本发明的催化剂。以这种方式，广泛得多的底物范围可以在低得多的温度下以空前高的选择性和产率转化。此外，只需要催化量的过渡金属，而Nisson的方法需要绝对化学计量量的铜。
本发明的催化剂系统优选包含两种金属成分。第一种成分优选包含可以采取两个相差一价的氧化态的金属，优选选自Ag(0，I)、Cu(0，I，II)、Mn(II，III)、Fe(II，III)、Co(II，III)、Ni(II，III)、Mo(IV，V)、Ru(II，III)(括号中示例了适合的氧化态组合)。金属可以任选以单质形式、作为络合物或作为盐使用。特别优选使用铜化合物或银化合物并还特别优选使用铜(I)化合物。
第二种成分的特征在于，其包含可以采取两个相差两价的氧化态的金属，优选选自Pd(0，II)、Ni(0，II)、Fe(-II，0，II)、Au(I，III)，Rh(I，III)、Pt(0，II，IV)、Ru(0，II)、Ir(I，III)(括号中示例了适合的氧化态组合)。金属可以任选以单质形式、作为络合物或作为盐使用。特别优选使用铂族金属，还特别优选使用钯化合物并更特别优选使用乙酰丙酮化钯(II)。
两种金属可以彼此独立地任选通过其它配体，优选选自胺、膦、N-杂环碳烯、腈或烯烃稳定化。特别优选使用环胺作为配体，还特别优选使用选自菲咯啉、联吡啶和三联吡啶或其取代衍生物的螯合性环胺。
任选通过在反应混合物中加入以上列举的成分而由适合的金属前体制备适合的催化剂。
在本发明的方法中可以使用通式I的羧酸盐，其中n、m、q、p是1至6之间的数且r是0至6之间的数，
在此反离子M(m+)任选是金属阳离子，优选选自金属Li、Na、K、Mg、Ca、B、Al、Ag、Cu、Mn、Fe、Co、Ni、Mo、Ru或有机阳离子，优选选自铵、吡啶鎓、磷鎓。任选除了羧酸盐外还可以配位另一种阴离子，优选选自I-、Br-、Cl-、F-、CO3 -、CN-、OH-、氧烷基-、HCO3 -、PO4 3-、HPO4 2-、H2PO4 -。
将所述的羧酸盐任选以预制成形式加入或由羧酸与适合的碱原位制备。
取代基R为有机基团，优选可选自直链、支链和环状C1-C20-烷基、直链、支链和环状C2-C20-链烯基以及C6-C20-芳基和选自吡啶、嘧啶、哒嗪、吡嗪、三嗪、四嗪、吡咯、吡唑、异噁唑、咪唑、噁唑、三唑、噻吩、呋喃的杂芳基并本身可以带有选自直链、支链和环状C1-C10-烷基；直链、支链和环状C2-C20-链烯基以及C6-C10-芳基和杂芳基；直链、支链和环状C1-C10-烷氧基或C1-C10-芳氧基；直链、支链和环状C1-C10-烷基-或C1-C10-芳基氨基羰基；直链、支链和环状C1-C10-酰基；直链、支链和环状C1-C10-二烷基氨基、C1-C10-芳基氨基、甲酰基、氧、硫、羟基、羧基、硝基、氰基、亚硝基和卤素如F、Cl、Br和I的其它取代基。
特别优选地，R可选自直链、支链和环状C2-C10-链烯基-、C6-C10-芳基或选自吡啶、嘧啶、哒嗪、吡嗪、三嗪、四嗪、吡咯、吡唑、异噁唑、咪唑、噁唑、噻唑、噻吩、呋喃的杂芳基并本身可以带有如上段所述的其它取代基。
R1-X(II)
在碳亲电子试剂R1-X(通式II)中，取代基X是常见的离去基团并优选选自：卤化物以及选自甲苯磺酸根、甲基磺酸根、三氟磺酸根、三氟乙酸根、羧酸根和[N2]+的假卤化物。
根据本发明的方法，碳亲电子试剂(通式II)中的取代基R1是有机基团并优选可选自直链、支链和环状C1-C20-烷基；直链、支链或环C2-C20-链烯基以及C6-C20-芳基和选自吡啶、嘧啶、哒嗪、吡嗪、三嗪、四嗪、吡咯、吡唑、异噁唑、咪唑、噁唑、噻唑、噻吩、呋喃的杂芳基并本身可以带有选自直链、支链和环状C1-C10-烷基；直链、支链和环状C2-C20-链烯基以及C6-C10-芳基和杂芳基；直链、支链和环状C1-C10-烷氧基或C1-C10-芳氧基；直链、支链和环状C1-C10-烷基-或C1-C10-芳基氨基羰基；直链、支链和环状C1-C10-酰基；直链、支链和环状C1-C10-二烷基氨基；C1-C10-芳基氨基、甲酰基、氧、硫、羟基、羧基、硝基、氰基、亚硝基和卤素如F、Cl、Br和I的其它取代基。
特别优选地，R1可选自直链、支链和环状C2-C10-链烯基-、C6-C10-芳基或选自吡啶、嘧啶、哒嗪、吡嗪、三嗪、四嗪、吡咯、吡唑、异噁唑、咪唑、噁唑、三噻唑、噻吩、呋喃的杂芳基并本身可以带有如上段所述的其它取代基。
或者，碳亲电子试剂可以是羰基衍生物，优选选自羰酰氯、羧酸酐、醛、酮、酯、α，β-不饱和醛、α，β-不饱和酮、α，β-不饱和酯。
根据本发明的方法，两种催化剂彼此独立地以基于碳亲电子试剂为0.001mol％至100mol％的量，优选以0.001mol％至10mol％的量并特别优选0.01mol％至5mol％的量使用。
本发明的方法在20℃至220℃，优选80℃至200℃并更优选在120℃至160℃的温度实施。
本发明的方法可以在溶剂存在下或在本体中实施。例如可以使用投入物料、直链、环状和支链烃(例如己烷、庚烷和辛烷)、芳香烃(例如苯、甲苯、二甲苯、乙苯、均三甲苯)、醚(例如1，4-二氧六环、四氢呋喃、甲基四氢呋喃、二丁基醚、甲基叔丁基醚、二异丙基醚、二乙二醇二甲醚)、酯(例如乙酸乙酯、乙酸丁酯)、酰胺(例如，二甲基甲酰胺、二乙基甲酰胺、N-甲基吡咯烷酮、二甲基乙酰胺)、二甲基亚砜、环丁砜、乙腈、异丁腈、丙腈、碳酸丙烯酯和卤代脂肪和芳香烃中的一种作为溶剂。
优选使用二甲基甲酰胺、二乙基甲酰胺、N-甲基吡咯烷酮、二甲基乙酰胺、二甲基亚砜、环丁砜、乙腈和碳酸丙烯酯。
本发明的方法优选这样实施，即通过常用的方法分离出反应期间的痕量水，例如通过蒸馏或通过加入水结合剂。
本发明的另一个主题为用于羧酸盐与碳亲电子试剂脱羧形成C-C键的催化剂系统，所述的催化剂系统由两种过渡金属或过渡金属化合物和选自菲咯啉、联吡啶和三联吡啶的任选取代的螯合性环胺组成。过渡金属优选选自所谓的贵金属，尤其是选自钯或钯化合物和铜或铜化合物。
实施例1-18
由实施例1-18看出，使用碳酸铜(II)和钯膦络合物的组合在120°的特别低的温度下达到出色的交叉偶联产物产率。使用的过渡金属化合物在反应混合物中还原为低级氧化态。可以认为铜作为Cu(I)化合物存在和钯作为Pd(0)存在。
由此根据表1，每种情况下首先使用化学计量量的碱将1.5mmol邻硝基苯甲酸去质子化。将得到的羧酸盐与1.0mmol4-氯-1-溴苯在钯(II)盐(0.02mmol)，任选配体(0.06mmol)和/或添加剂(1.5mmol)存在下在3ml溶剂中于120℃搅拌24h。在有些情况下，将反应混合物通过加入500mg分子筛(3)而干燥。使用正十四碳烷作为内标物质借助气相色谱测定产率。
示意图3.制备2-硝基-4’-氯联苯
实施例 Pd源 配体 溶剂 碱 添加剂 产率(％)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Pd(acac)2 PdCl2 Pd(OAc)2 Pd(acac)2 Pd(acac)2 Pd(acac)2 Pd(acac)2 Pd(acac)2 Pd(acac)2 Pd(acac)2 Pd(acac)2 Pd(acac)2 Pd(acac)2 Pd(acac)2 Pd(acac)2 Pd(acac)2 Pd(acac)2 Pd(acac)2 PPh3 PPh3 PPh3 PPh3 PPh3 PPh3 PPh3 PPh3 BINAP DPPF P(p-MeOPh)3 P(Cy)3 联吡啶 P(i-propyl)Ph2 P(i-propyl)Ph2 P(i-propyl)Ph2 P(i-propyl)Ph2 P(i-propyl)Ph2 NMP NMP NMP NMP NMP NMP NMP NMP NMP NMP NMP NMP NMP NMP NMP DMSO DMPU 二乙二醇二 甲醚 CuCO3 CuCO3 CuCO3 CuCO3 CuCO3 CuCO3 CuCO3 CuCO3 CuCO3 CuCO3 CuCO3 CuCO3 CuCO3 CuCO3 Ag2CO3 CuCO3 CuCO3 CuCO3 - - - KBr NaF LiF KF KF/3 MS KF/3 MS KF/3 MS KF/3 MS KF/3 MS KF/3 MS KF/3 MS KF/3 MS KF/3 MS KF/3 MS KF/3 MS 9 3 5 14 16 15 32 84 76 70 71 60 35 98 45 69 62 40
i-propyl＝异丙基
实施例19-25
由实施例19-25、表2看出在第二种方法变体中，已经使用非常少量的包含铜(I)盐、钯(II)盐和胺配体的催化剂系统以较高的效率实现了原位制备的羧酸钾与芳基卤的反应。在此每种情况下首先使用化学计量量的碳酸钾将1.5mmol的邻硝基苯甲酸去质子化并蒸馏除去反应水。然后将得到的羧酸盐与1.0mmol的4-氯-1-溴苯在0.02mmol的乙酰丙酮化钯(II)存在下，将给定量的氯化亚铜(I)和给定量的胺配体在NMP中于160℃搅拌24h。在此通过加入500mg分子筛(3)结合可能残留的水分。使用正十四碳烷作为内标物质借助气相色谱测定产率。
表2
实施例 Pd(acac)2 (mmol) 配体(mmol) Cu盐 (mmol) 产率 (％)
19 20 21 22 23 24 25 0.02 0.02 0.02 0.02 0.02 0.01 0.005 联吡啶(0.1) 联吡啶(0.1) 联吡啶(0.1) 4，4’-二甲基-2，2’-联 吡啶(0.1) 菲咯啉(0.1) 菲咯啉(0.05) 菲咯啉(0.05) CuI(0.1) CuBr(0.1) CuCl(0.1) CuI(0.1) CuI(0.1) CuI(0.03) CuI(0.01) 99 95 95 98 99 97 80
实施例26-55
根据示意图5以1mmol的量实施表3的实施例26-55，来证明本发明方法的广泛适用性。将产物在含水处理后，经硅胶色谱分析测定产率并借助NMR，MS，HRMS清楚地表征。
示意图5
表3
isopropyl＝异丙基
使用催化量的铜和催化量的钯的实施例
根据示意图5使用1mmol的芳基溴和1.2mmol的羧酸实施表4的实施例56-71，来证明不依赖于底物只需要催化量的两种过渡金属。将产物在含水处理后，经硅胶色谱分析测定产率并借助NMR，MS，HRMS清楚地表征。
示意图5

Claims (13)

1.通过羧酸盐与碳亲电子试剂在过渡金属或过渡金属化合物作为催化剂系统存在下反应脱羧形成C-C键的方法，所述羧酸盐选自通式1的化合物，
其中n、m、q、p为1和6之间的数且r为0和6之间的数，M(m+)为金属阳离子或有机阳离子，所述金属选自Li、Na、K、Mg、Ca、B、Al、Ag、Cu、Mn、Fe、Co、Ni、Mo、Ru，所述有机阳离子选自铵、吡啶鎓、磷鎓，Y(P-)为阴离子，其选自I-、Br-、Cl-、F-、CO3 -、CN-、OH-、氧烷基-、HCO3 -、PO4 3-、HPO4 2-、H2PO4 -，R为有机基团选自直链、支链和环状C2-C20-链烯基，以及C6-C20-芳基和选自吡啶、嘧啶、哒嗪、吡嗪、三嗪、四嗪、吡咯、吡唑、异噁唑、咪唑、噁唑、噻唑、噻吩、呋喃的杂芳基，并本身可以带有选自直链、支链和环状C1-C10-烷基；直链、支链和环状C2-C20-链烯基以及C6-C10-芳基和杂芳基；直链、支链和环状C1-C10-烷氧基或C1-C10-芳氧基；直链、支链和环状C1-C10-烷基-或C1-C10-芳基氨基羰基；直链、支链和环状C1-C10-酰基；直链、支链和环状C1-C10-二烷基氨基、C1-C10-芳基氨基、甲酰基、氧、硫、羟基、羧基、硝基、氰基、亚硝基和选自F、Cl、Br和I的卤素的其它取代基；
所述碳亲电子试剂相应于通式R1-X，其中取代基X可选自：选自I、Br、Cl的卤化物和选自甲苯磺酸根、甲基磺酸根、三氟磺酸根、三氟乙酸根、羧酸根或[N2]+的假卤化物，并且其中碳亲电子试剂的取代基R1选自直链、支链和环状C2-C20-链烯基，以及C6-C20-芳基和选自吡啶、嘧啶、哒嗪、吡嗪、三嗪、四嗪、吡咯、吡唑、异噁唑、咪唑、噁唑、噻唑、噻吩、呋喃的杂芳基，并本身可以带有选自直链、支链和环状C1-C10-烷基；直链、支链和环状C2-C20-链烯基以及C6-C10-芳基和杂芳基；直链、支链和环状C1-C10-烷氧基或C1-C10-芳氧基；直链、支链和环状C1-C10-烷基-或C1-C10-芳基氨基羰基；直链、支链和环状C1-C10-酰基；直链、支链和环状C1-C10-二烷基氨基、C1-C10-芳基氨基、甲酰基、氧、硫、羟基、羧基、硝基、氰基、亚硝基和选自F、Cl、Br和I的卤素的其它取代基，其中催化剂系统包含两种不同的过渡金属和/或过渡金属化合物，其中一种过渡金属选自Ag或Cu，并且其中另一过渡金属为Pd。
2.根据权利要求1的方法，其中第一种过渡金属化合物为铜(I)盐。
3.根据权利要求1的方法，其中其它的过渡金属化合物为乙酰丙酮化钯(II)。
4.根据权利要求1的方法，其中至少一种金属通过选自胺、膦、N-杂环碳烯、腈、烯烃的其它配体而稳定化。
5.根据权利要求4的方法，其中使用环胺作为配体。
6.根据权利要求4的方法，其中所述的配体为选自菲咯啉、联吡啶和三联吡啶的任选取代的螯合性环胺。
7.根据权利要求1的方法，其中所述两种不同的过渡金属和/或过渡金属化合物彼此独立地以基于碳亲电子试剂为0.001mol％至100mol％的量使用。
8.根据权利要求1的方法，其中所述两种不同的过渡金属和/或过渡金属化合物彼此独立地以基于碳亲电子试剂为0.01mol％至5mol％的量使用。
9.根据权利要求1-8中任一项的方法，其中反应温度为80℃至200℃。
10.根据权利要求9的方法，其中反应温度为120℃至160℃。
11.根据权利要求1-8中任一项的方法，其中反应期间除去痕量水。
12.根据权利要求1-8中任一项的方法，其中碳亲电子试剂为选自羰酰氯、羧酸酐、醛、酮、酯、α，β-不饱和醛、α，β-不饱和酮、α，β-不饱和酯的羰基衍生物。
13.使羧酸盐与相应于通式R1-X的碳亲电子试剂脱羧形成C-C键的催化剂系统，所述的催化剂系统由钯化合物和铜化合物和选自菲咯啉、联吡啶和三联吡啶的任选取代的螯合性环胺组成，所述羧酸盐选自通式1的化合物，其中n、m、q、p、r、M(m+)、R、Y(P-)、X、R1具有在权利要求1至12中任一项所给出的含义，
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