Development of Amphiphilic Resin-Supported Catalysts Realizing Water-Based Organic Synthesis

以聚乙二醇-聚苯乙烯接枝共聚物（PEG-PS）为载体，设计并合成了新型两亲性树脂支载三芳基膦（PEP）。PEG-PS树脂负载的钯-单膦络合物Pd（PEP）通过用过量的二（间氯）双（H3-烯丙基）二钯（II）（[PdCl（H3-C3 H5）]2）（Pd/P > 1/1）处理PEP，随后通过洗涤除去未固定的[PdCl（H3-C3 H5）]2而容易地制备。钯-Pd（PEP）催化的3-乙酰氧基-1，3-二苯基-1-丙烯和乙酸肉桂酯与各种亲核试剂（包括1，3-二羰基化合物、氨基酸、sodiumazide和亚磺酸钠）的烯丙基取代反应，在碱性水溶液中，在常压下，芳基或烯基卤化物的羟羰基化反应也发生在碱性水溶液中，一氧化碳含量25 C在3mol%钯的两亲性树脂负载的钯-膦配体的存在下， ...更多信息 聚乙二醇-聚苯乙烯接枝共聚物（PEG-PS树脂）（Pd（PEP）.卤代芳烃的反应定量地得到相应的苯甲酸。Pd-PEP催化碘苯与丙烯酸的Heck反应合成肉桂酸，收率92%。反应中不使用有机溶剂，不需要色谱纯化即可获得产物。通过过滤回收树脂负载的催化剂并重复使用。在30次运行期间没有观察到催化活性的损失。在水溶液中，以Pd（PEP）为催化剂，研究了芳基卤、乙酸烯丙酯与芳基硼酸、四苯硼钠的交叉偶联反应。在25 ℃碱性水溶液中，在2mol%钯或钯（PEP）存在下，芳基卤与芳基硼试剂反应。C以高产率得到相应的联苯衍生物。Pd（PEP）还催化乙酸烯丙酯（包括乙酸1，3-二取代烯丙酯和乙酸环烯丙酯）与芳基硼试剂在水中的烯丙基芳基化反应，在类似的反应条件下，得到80-99%产率的烯丙基芳烃。少

New amphiphilic resin-supported triarylphosphines (PEP) were designed and prepared on polyethylene glycol-polystyrene graft copolymer (PEG-PS). The PEG-PS resin-supported palladium-monophosphine complex Pd(PEP) was readily prepared by treatment of PEP with an excess amount of di(m-chloro)bis(h3-allyl) dipalladium(II) ([PdCl(h3-C3H5)]2) (Pd/P > 1/1) followed by removal of unimmobilized [PdCl(h3-C3H5)]2 by washing. Palladium complexe Pd(PEP) catalyzed allylic substitution of 3-acetoxy-1,3-diphenyl-1-propene and cinnamyl acetate with various nucleophiles including 1,3-dicarbonyl compounds, amino acids, sodiumazide, and sodium sulfinate, to give quantitative yields of corres ponding allylic substituted products in water.The hydroxycarbonylation reaction of aryl or alkenyl halides also took place in aqueous alkaline solution under an atmospheric pressure of carbon monoxide at 25 。C in the presence of 3 mol % palladium of an amphiphilic resin-supported palladium-phosphine complexe bound to a … More polyethylene glycol-polystyrene graft copolymer (PEG-PS resin) (Pd(PEP). The reaction of aryl halides gave correspond-ing benzoic acids in quantitative yields. Pd-PEP also catalyzedHeck reaction of iodobenzene with acrylic acid to give cinnamic acid in 92%yield. No organic solvent was used for the reactions and no chromatographical purification was re-quired to obtain the products. The resin-supported catalyst was recovered by filtration and reused. No loss of catalytic activity was observed during 30 runs. The cross-coupling reaction of aryl halides or allyl acetates with arylboronic acids or sodium tetraphenylborate was catalyzed in water by the Pd(PEP) catalyst. The reaction of aryl halides with arylboron reagents in the presence of 2 mol% palladium of Pd(PEP) in aqueous alkaline solution at 25 。C gave corresponding biphenyl derivatives in high yields. Pd(PEP) also catalyzed allylic arylation of allyl acetates (including 1,3-disubstituted allyl acetates and cyclic allyl acetates) with arylboron reagents in water under the similar reaction conditions to give 80-99% yield of allylarenes. Less