四膦配体/钯体系催化无铜Sonogashira偶联反应
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摘要
以环己二胺为骨架的含氮四膦配体N,N,N',N'-四[(二苯基膦)甲基]环己二胺和钯组成的催化体系用于苯乙炔和芳卤的Sonogashira反应,该催化体系对卤代芳烃显示了良好的官能团容忍性。结果显示空间位阻的影响大于电子效应,通常能与金属配位使得金属催化剂失活而难以顺利反应的含N杂环化合物,3-溴喹啉以99%的收率获得相应的产物,活性较低的氯代底物,3-氯吡啶的目标产物产率为90%。
The catalytic performance of tetraphosphine based on cyclohexanediamine as backbone N,N,N',N'-tetra-[( diphenylphosphino) methyl] cyclohexanediamine combined with palladium for Sonogashira reaction of aryl halides with phenylacetylene was investigated. The results showed that the catalytic system had good functional tolerance and the effect of steric hindrance was greater than electron effect. For N-heterocyclic compounds,the reaction was usually difficult to happen cause N could coordination with metal,but the yield of 99% was obtained with 3-bromoquinoline.With lower active chlorine substrates,the yield of the target product of 3-chlorobridine was 90%.
The catalytic performance of tetraphosphine based on cyclohexanediamine as backbone N,N,N',N'-tetra-[( diphenylphosphino) methyl] cyclohexanediamine combined with palladium for Sonogashira reaction of aryl halides with phenylacetylene was investigated. The results showed that the catalytic system had good functional tolerance and the effect of steric hindrance was greater than electron effect. For N-heterocyclic compounds,the reaction was usually difficult to happen cause N could coordination with metal,but the yield of 99% was obtained with 3-bromoquinoline.With lower active chlorine substrates,the yield of the target product of 3-chlorobridine was 90%.
引文
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[2]汪方瑰,黄凯智,关金涛,等. N-甲基咪唑膦/钯催化Sonogashira偶联反应研究[J].广州化工,2017(14):68-70.
[3]G Evano, N Blanchard, M Toumi. Copper-Mediated Coupling Reactions and Their Applications in Natural Products and Designed Biomolecules Synthesis[J]. Chem. Rev.,2008,108:3054-3131.
[4]王贤.炔铜促进非贵金属催化Sonogashira偶联反应研究[D].陕西师范大学,2017.
[5]T Hundertmark,A F Littke,S L Buchwald. Pd(PhCN)2Cl2/P(tBu)3:A Versatile Catalyst for Sonogashira Reactions of Aryl Bromides at Room Temperature[J]. Org. Lett.,2000,2:1729-1731.
[6]B H Lipshutz,D W Chung,B Rich. Sonogashira Couplings of Aryl Bromides:Room Temperature,Water Only,No Copper[J]. Org.Lett.,2008,10:3793-3796.
[7]M Feuerstein, F Berthio, M Santelli. Palladium-tetraphosphine complex:an efficient catalyst for the coupling of aryl halides with alkynes[J]. Org. Biomol. Chem.,2003,1(13):2235-2237.
[8]X J Yu,R Zhou,R X Li,et al. Heck coupling reaction catalyzed by[(C3H5)PdCl]2-N,N,N',N'-tetra(diphenylphosphinomethyl)-1,2-ethylenediamine[J]. Catal. Commun.,2010,12(3):222-225.
[9]Tsuji J,Iwamoto N. Organic synthesis by means of noble-metal compounds. The mechanism of simultaneous formation of isocyanate andπ-allylpalladium chloride from sodium chloropalladate,allyl chloride,primary amine,and carbon monoxide[J]. Chem. Commun.,1966:828-829.
[10]Yiping Z,Yuan Z,Puddephatt R J. Allyl(β-diketonato)palladium(Ⅱ)Complexes,Including Liquid Precursors,for Chemical Vapor Deposition of Palladium[J]. Chem. Mater.,1998:2293-2300.
[11]Tatsuno Y,Yoshida T,Otsuka S.(η3-Allyl)palladium(Ⅱ)complexes[J]. Inorg. Synth.,1990,28:342-345.