钯催化氧气氧化带吸电子基团烯烃的反应研究
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摘要
石油是世界上药品、农用化学品到大规模化学品等有机化工产业生产的主要原料。石油主要由还原型的碳氢化合物组成,因此它们的选择性氧化反应研究就成为化学工业中最重要的挑战性课题之一。钯催化氧气氧化反应的繁荣始于上世纪50年代末,即著名的PdCl_2/CuCl_2/O_2体系催化氧化乙烯制备乙醛的Wacker工艺的开创。从那以后,人们对钯催化氧气氧化反应的研究热情从未间断。
钯催化的氧气氧化反应过程一般可分为两个步骤:1)Pd(II)对反应底物的氧化;2)O_2对Pd(0)的再氧化以实现催化剂的再生。对于成功的钯催化氧气氧化反应来说,关键问题在于:怎样使氧气高效地氧化还原态的Pd(0)物种。从热力学角度看,氧气可以氧化Pd(0)至Pd(II),但是从动力学角度看,Pd(0)有聚合形成没有活性的Pd金属块的趋向。怎样解决这样一个矛盾就衍生出现今各国科学家开发的各种各样的Pd催化O_2氧化反应的有效体系。一方面,在体系中加入助氧化剂作为中介体系,将氧气氧化还原态Pd(0)的热力学能垒通过助剂的氧化还原循环中介而分解成更小的一到多个能垒。通过这些中介形成同动力学方向上有利的Pd(0)失效聚合竞争反应的比较优势,而在整个氧化过程中,氧气仍然作为体系中唯一被最终消耗的氧化剂;另一方面,在体系中加入适当配体,增加反应过程中因催化氧化反应底物而生成的还原态Pd(0)的稳定性,使得O_2可以充分将其氧化而抑制Pd(0)的聚合失效。
在此背景下,本论文成功研发了两组不同的无助剂钯催化氧气氧化体系Pd(II)/O_2/ scCO_2(MeOH)和Pd(II)/DMF/O_2,并通过对体系条件的控制,实现了一系列带吸电子基团烯烃的选择性氧化反应:
1、在Pd(II)/O_2/scCO_2(MeOH)体系中,当使用过量MeOH,在较高氧气浓度和较低温度下,实现了带吸电子基团烯烃的缩醛化反应。该体系与先前需CuCl_2中介的催化体系相比,避免了大量氯离子的存在,有利于β-氢消除过程,因此有利于缩醛化反应,同时有效地抑制了Michael加成产物。
2、在Pd(II)/O_2/scCO_2(MeOH)体系中,当使用适量MeOH,在较低氧气浓度和较高温度下,实现了带吸电子基团烯烃的三聚反应。这一方法具有重要合成意义,它突破了先前芳构化反应区域选择性以及底物为炔烃的局限性,只利用廉价易得的烯烃为原料,具有更高的潜在工业应用价值。
3、在Pd(II)/DMF/O_2体系中,在严格除水的条件下,能够实现一系列α位带有羰基的末端烯烃,包括烷基烯烃和芳基烯烃在内的三聚反应,高区域选择性生成1,3,5-三取代苯衍生物。相比在Pd(II)/O_2/scCO_2(MeOH)体系中实现的末端烯烃三聚反应,由于助溶剂MeOH的缺失,使得体系没有缩醛副产物的生成,并且使用丙烯酸苯酯等芳基底物时,也避免了与MeOH的酯交换副反应,可以顺利得到中心对称的含有四个苯环的化合物。这些化合物在高分子化学领域具有非常重要的用途,是合成星形聚合物的前驱体。
4、在Pd(II)/DMF/O_2体系中,在不除水的条件下,我们首创了利用二甲基甲酰胺DMF水解原位瞬时生成的PdCl_2(HNMe_2)_2催化炔酸酯和带吸电子基团烯烃,高选择性的发生[2+2+2]交叉三聚反应,以2:1的氧化偶联方式生成五取代苯衍生物的方法。此过程使得三聚方法中传统的炔烃替代物从特殊的带有易离去基团的烯烃发展为分子氧存在下的简单烯烃,并且先前烯烃单组份体系中不能发生三聚反应的烯烃,包括丙烯腈,丙烯酸,丙烯酰胺衍生物等,都可以顺利地与炔酯发生交叉三聚产物,并且芳构化产品的收率得到了较大的提高。
Petroleum feedstocks serve as the primary source of the world’s industrial organic chemicals, ranging from pharmaceuticals and agrochemicals to large-scale commodity products. Petroleum primarily consists of reduced hydrocarbons, and their selective oxidation chemistry remains one of the foremost challenges in the chemical industry. Since the discovery of the notably PdCl_2/CuCl_2/O_2 catalyzed Wacker oxidation which transfers terminal alkenes to corresponding aldehyde in the late 1950s, enthusiasm for the Pd catalyzed aerobic oxidation reactions has never stopped.
Pd catalyzed aerobic oxidation is generally divided into two steps: 1) selective oxidation of the organic substrate by the oxidized catalyst and 2) efficient dioxygen-coupled reoxidation of the reduced catalyst. The key to the success of Pd catalyzed aerobic oxidation is to solve the fundamentally key problem: how to effectively get the reduced catalyst spieces Pd (0) oxidized to Pd (II) by molecular oxygen. Thermodynamically, molecular oxygen is capable of oxidizing reduced Pd (0) spieces to active Pd (II) catalyst, however, direct aerobic oxidation of palladium often cannot compete with kinetically aggregation of the Pd (0) spieces into inactive bulk metal. How to solve such a contradiction derivativats the two strategies for palladium catalyzed aerobic oxidation. One is to add cocatalyst systems to break down the thermodynamic energy barrier of oxidation of Pd (0) by molecular oxygen into smaller ones; The other is to add a Ligand system which will stable the Pd(0) spieces and hold back its aggregation.
In this contest, we have developed two different Palladium catalyzed aerobic oxidation systems with molecular oxygen as the sole oxidatant: PdII/O_2/scCO_2(MeOH) system and PdII/DMF/O_2 system, and product control of palladium-catalyzed aerobic oxidation of terminal olefins with electron-withdrawing groups can be achieved through modifying the catalytic system conditions:
1, PdII/O_2/scCO_2 (MeOH) system, when using excess MeOH, higher pressure of oxygen and lower temperature, acetalization of olefin with electron withdrawing groups can be achieved. Compared with previous catalytic system with CuCl_2 as a cocatalyst, it successfully avoids the presence of a large number of chloride ions, which is beneficial to the process ofβ-hydride elimination, thereby facilitating the formation of acetals, and also effectively inhibited the Michael addition product.
2, PdII/O_2/scCO_2 (MeOH) system, when using appropriate dosage of MeOH, lower pressure of oxygen and higher temperature, cyclotrimerization of terminal olefin with electron -withdrawing groups can be achieved. This approach is of great synthetic significance, it broke through the regioselectivity and substrate limitations for cyclotrimerization of alkynes. It only uses the cheap and readily available olefins as raw materials and posess a higher potential value in industry application.
3, PdII/DMF/O_2 system, when the reaction system was strictly dryed, cyclotrimerization ofα-carbonyl terminal olefin can be achieved. Both the alkyl and aryl olefins can be cyclotrimerized to 1,3,5-trisubstituted benzene derivatives. Compared to the PdII/O_2/scCO_2 (MeOH) system, the lack of MeOH avoids the acetalization and transesterification. These 1,3,5-trisubstituted benzene derivatives are very important initiators in the field of polymer chemistry to the synthesis of well-defined star polymers.
4, PdII/DMF/O_2 system, when the reaction system was not dried, we have established an in situ DMF hydrolysis producing PdCl_2(HNMe_2)_2 to catalyze highly selective 2: 1 cross [2+2 +2] cycloaddition of alkynoates and alkenes with electron-withdrawing groups under molecular oxygen to synthesize pentakis-substituted benzenes. This methodology not only makes an extension of alkyne surrogates from special alkenes with leaving groups to simple alkenes under molecular oxygen, but also makes the olefins which can not cyclotrimerize in the the previous one-component system, including acrylonitrile, acrylic acid, and acrylamide derivatives, oxidatively coupled with alkynoates to smoothly yield aromatic products in good to excellent yields.
钯催化的氧气氧化反应过程一般可分为两个步骤:1)Pd(II)对反应底物的氧化;2)O_2对Pd(0)的再氧化以实现催化剂的再生。对于成功的钯催化氧气氧化反应来说,关键问题在于:怎样使氧气高效地氧化还原态的Pd(0)物种。从热力学角度看,氧气可以氧化Pd(0)至Pd(II),但是从动力学角度看,Pd(0)有聚合形成没有活性的Pd金属块的趋向。怎样解决这样一个矛盾就衍生出现今各国科学家开发的各种各样的Pd催化O_2氧化反应的有效体系。一方面,在体系中加入助氧化剂作为中介体系,将氧气氧化还原态Pd(0)的热力学能垒通过助剂的氧化还原循环中介而分解成更小的一到多个能垒。通过这些中介形成同动力学方向上有利的Pd(0)失效聚合竞争反应的比较优势,而在整个氧化过程中,氧气仍然作为体系中唯一被最终消耗的氧化剂;另一方面,在体系中加入适当配体,增加反应过程中因催化氧化反应底物而生成的还原态Pd(0)的稳定性,使得O_2可以充分将其氧化而抑制Pd(0)的聚合失效。
在此背景下,本论文成功研发了两组不同的无助剂钯催化氧气氧化体系Pd(II)/O_2/ scCO_2(MeOH)和Pd(II)/DMF/O_2,并通过对体系条件的控制,实现了一系列带吸电子基团烯烃的选择性氧化反应:
1、在Pd(II)/O_2/scCO_2(MeOH)体系中,当使用过量MeOH,在较高氧气浓度和较低温度下,实现了带吸电子基团烯烃的缩醛化反应。该体系与先前需CuCl_2中介的催化体系相比,避免了大量氯离子的存在,有利于β-氢消除过程,因此有利于缩醛化反应,同时有效地抑制了Michael加成产物。
2、在Pd(II)/O_2/scCO_2(MeOH)体系中,当使用适量MeOH,在较低氧气浓度和较高温度下,实现了带吸电子基团烯烃的三聚反应。这一方法具有重要合成意义,它突破了先前芳构化反应区域选择性以及底物为炔烃的局限性,只利用廉价易得的烯烃为原料,具有更高的潜在工业应用价值。
3、在Pd(II)/DMF/O_2体系中,在严格除水的条件下,能够实现一系列α位带有羰基的末端烯烃,包括烷基烯烃和芳基烯烃在内的三聚反应,高区域选择性生成1,3,5-三取代苯衍生物。相比在Pd(II)/O_2/scCO_2(MeOH)体系中实现的末端烯烃三聚反应,由于助溶剂MeOH的缺失,使得体系没有缩醛副产物的生成,并且使用丙烯酸苯酯等芳基底物时,也避免了与MeOH的酯交换副反应,可以顺利得到中心对称的含有四个苯环的化合物。这些化合物在高分子化学领域具有非常重要的用途,是合成星形聚合物的前驱体。
4、在Pd(II)/DMF/O_2体系中,在不除水的条件下,我们首创了利用二甲基甲酰胺DMF水解原位瞬时生成的PdCl_2(HNMe_2)_2催化炔酸酯和带吸电子基团烯烃,高选择性的发生[2+2+2]交叉三聚反应,以2:1的氧化偶联方式生成五取代苯衍生物的方法。此过程使得三聚方法中传统的炔烃替代物从特殊的带有易离去基团的烯烃发展为分子氧存在下的简单烯烃,并且先前烯烃单组份体系中不能发生三聚反应的烯烃,包括丙烯腈,丙烯酸,丙烯酰胺衍生物等,都可以顺利地与炔酯发生交叉三聚产物,并且芳构化产品的收率得到了较大的提高。
Petroleum feedstocks serve as the primary source of the world’s industrial organic chemicals, ranging from pharmaceuticals and agrochemicals to large-scale commodity products. Petroleum primarily consists of reduced hydrocarbons, and their selective oxidation chemistry remains one of the foremost challenges in the chemical industry. Since the discovery of the notably PdCl_2/CuCl_2/O_2 catalyzed Wacker oxidation which transfers terminal alkenes to corresponding aldehyde in the late 1950s, enthusiasm for the Pd catalyzed aerobic oxidation reactions has never stopped.
Pd catalyzed aerobic oxidation is generally divided into two steps: 1) selective oxidation of the organic substrate by the oxidized catalyst and 2) efficient dioxygen-coupled reoxidation of the reduced catalyst. The key to the success of Pd catalyzed aerobic oxidation is to solve the fundamentally key problem: how to effectively get the reduced catalyst spieces Pd (0) oxidized to Pd (II) by molecular oxygen. Thermodynamically, molecular oxygen is capable of oxidizing reduced Pd (0) spieces to active Pd (II) catalyst, however, direct aerobic oxidation of palladium often cannot compete with kinetically aggregation of the Pd (0) spieces into inactive bulk metal. How to solve such a contradiction derivativats the two strategies for palladium catalyzed aerobic oxidation. One is to add cocatalyst systems to break down the thermodynamic energy barrier of oxidation of Pd (0) by molecular oxygen into smaller ones; The other is to add a Ligand system which will stable the Pd(0) spieces and hold back its aggregation.
In this contest, we have developed two different Palladium catalyzed aerobic oxidation systems with molecular oxygen as the sole oxidatant: PdII/O_2/scCO_2(MeOH) system and PdII/DMF/O_2 system, and product control of palladium-catalyzed aerobic oxidation of terminal olefins with electron-withdrawing groups can be achieved through modifying the catalytic system conditions:
1, PdII/O_2/scCO_2 (MeOH) system, when using excess MeOH, higher pressure of oxygen and lower temperature, acetalization of olefin with electron withdrawing groups can be achieved. Compared with previous catalytic system with CuCl_2 as a cocatalyst, it successfully avoids the presence of a large number of chloride ions, which is beneficial to the process ofβ-hydride elimination, thereby facilitating the formation of acetals, and also effectively inhibited the Michael addition product.
2, PdII/O_2/scCO_2 (MeOH) system, when using appropriate dosage of MeOH, lower pressure of oxygen and higher temperature, cyclotrimerization of terminal olefin with electron -withdrawing groups can be achieved. This approach is of great synthetic significance, it broke through the regioselectivity and substrate limitations for cyclotrimerization of alkynes. It only uses the cheap and readily available olefins as raw materials and posess a higher potential value in industry application.
3, PdII/DMF/O_2 system, when the reaction system was strictly dryed, cyclotrimerization ofα-carbonyl terminal olefin can be achieved. Both the alkyl and aryl olefins can be cyclotrimerized to 1,3,5-trisubstituted benzene derivatives. Compared to the PdII/O_2/scCO_2 (MeOH) system, the lack of MeOH avoids the acetalization and transesterification. These 1,3,5-trisubstituted benzene derivatives are very important initiators in the field of polymer chemistry to the synthesis of well-defined star polymers.
4, PdII/DMF/O_2 system, when the reaction system was not dried, we have established an in situ DMF hydrolysis producing PdCl_2(HNMe_2)_2 to catalyze highly selective 2: 1 cross [2+2 +2] cycloaddition of alkynoates and alkenes with electron-withdrawing groups under molecular oxygen to synthesize pentakis-substituted benzenes. This methodology not only makes an extension of alkyne surrogates from special alkenes with leaving groups to simple alkenes under molecular oxygen, but also makes the olefins which can not cyclotrimerize in the the previous one-component system, including acrylonitrile, acrylic acid, and acrylamide derivatives, oxidatively coupled with alkynoates to smoothly yield aromatic products in good to excellent yields.
引文
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