Copper - based MOFs- catalyzed cyanation of Ar yl iodides
Author information+
(School of Chemistry and Chemical Engineering/Key Laboratory for Green Processing
of Chemical Engineering of Xinjiang Bingtuan, Shihezi University, Shihezi, Xinjiang 832003, China)
Organic cyanide is a kind of skeleton module which has important application in the field of organic synthesis, such
as in natural products, drug synthesis, dyes, pesticides and materials. However, there is no example using copper-based
metal-organic framework materials (Cu-MOF) as the catalyst for C-CN bond formation. Herein, four typical Cu-MOFs catalysts
were prepared according to the method of literature reports (the organic ligands are imidazole, 2-hydroxy pyrimidine, terephthalic
acid and trimesic acid), which was then applied to the halogenated aromatic cyanation reaction. After optimization, the
combination of 10 mol% MOF-199, 2 equiv. Na2CO3, and 50 mol% of K4Fe (CN)6
·3H2O at 140 ℃ for 24 h was the optimal
conditions, and the corresponding cyanation products were obtained with good to excellent yields. Moreover, the catalyst can be
reused at least 4 times without significantly decreasing of activity, which is great significance for developing and improving the
Cu-MOF catalyzed cyanation reaction.
Li Zihao, Shen Li, Xie Jianwei.
Copper - based MOFs- catalyzed cyanation of Ar yl iodides. Journal of Shihezi University. 2017, 35(2): 226-230 https://doi.org/10.13880/j.cnki.65- 1174/n.2017.02.016
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参考文献
[1] Dalton J R，Regen S L.Alumina assisted aryl cyanation[J].
Journal of Organic Chemistry，1979，44(24):4443-4444.
[2] Zanon J，Klapars A，Buchwald S L.Cooper-catalyzed domino halide exchange-cyanation of aryl bromides [J].Journal
of the American Chemical Society，2003，125(10):2890- 2891.
[3] Yang C，Williams J M.Palladium-catalyzed cyanation of
aryl bromides promoted by low-level organotin compounds
[J].Organic Letters，2004，6(17):2837-2840.
[4] Sundermeier M，Mutyala S，Zapf A，et al.A convenient and
efficient procedure for the palladium-catalyzed cyanation
of aryl halides using trimethylsilylcyanide[J].Journal of Organometallic Chemistry，2004，35(7):50-55.
[5] Marcantonio K M，Frey L F，Liu Y，et al.An investigation
into causes and effects of high cyanide levels in the palladiumcatalyzed cyanation reaction[J].Organic Letters，2004，
6(21):3723- 3725.
[6] Hatsuda M，Seki M.A practical synthesis of highly functionalized aryl nitriles through cyanation of aryl bromides
employing heterogeneous Pd/C[J].Tetrahedron Letters，2005，
46(11):1849- 1853.
[7] Sundermeier M，Zapf A，Beller M.A convenient procedure
for the palladium-catalyzed cyanation of aryl halides [J].
Angewandte Chemie International Edition，2003，42 (14):
1661-1664.[8] Schareina T，Zapf A，Beller M.Potassium hexacyanoferrate
(II)-a new cyanating agent for the palladium-catalyzed cyanation of aryl halides[J].Chemical Communications，2004，
(12):1388-1389.
[9] Schareina T，Zapf A，Beller M.Improving palladium-catalyzed cyanation of aryl halides:development of a state-of-theart methodology using potassium hexayanoferrate (II) as
cyanating agent [J].Journal of Organometallic Chemistry，
2004，689(24):4576-4583.
[10] Weissman S A，Zewge D，Chen C.Ligand-free palladiumcatalyzed cyanation of aryl halides [J].Journal of Organic
Chemistry，2005，70(4):1508-1510.
[11] Grossman O，Gelman D.Novel Trans-spanned palladium
complexes as efficient catalysts in mild and amine-free
cyanation of aryl bromides under air [J].Organic Letters，
2006，8(6):1189-1191.
[12] 贾超，原鲜霞，马紫峰.金属有机骨架化合物(MOFs)作为储
氢材料的研究进展[J].化学进展，2009，21(9):1954-1962.
Jia C，Yuan X X，Ma Z F.Metal-Organic Frameworks (MOFs)
as Hydrogen Storage Materials [J].Progress in Chemistry，
2009，21(5):1954-1962.
[13] 宋国强，王志清，王亮，等.MOF(Fe)的制备及其氧气还原催
化性能[J].催化学报，2014，35(2):185-195.
Song G Q，Wang Z Q，Wang L，et al.Preparation of MOF
(Fe) and its catalytic activity for oxygen reduction reaction
in an alkaline electrolyte [J].Chinese Journal of Catalysis，
2014，35(2):185-195.
[14] Jiang Y J，Huang J，Kasumaj B，et al.Adsorption Desorption
Induced Structural Changes of Cu-MOF Evidenced by Solid State NMR and EPR Spectroscopy [J].Journal of the
American Chemical Society，2009，131(6):2058-2059.
[15] 黎林清，吕迎，李军，等.金属 - 有机骨架材料在烯烃氧化
中的应用[J].化学进展，2012，24(5):747-756.
Li L Q，Lv Y，Li J，et al.Application of Metal-Organic Frameworks in Olefin Oxidation [J].Progress in Chemistry，
2012，24(5):747-756.
[16] Wang F，Yu R，Wu X，et al.A cationic copper-iodine cluster-based metal-organic framework (MOF) with (4，8)-connected fluorite topology[J].Inorganic Chemistry Communications，2012，19:70-72.
[17] Yang J，Liu Q，Sun W J.Co(II)-doped MOF-5 nano/microcrystals:Solvatochromic behaviour，sensing solvent molecules
and gas sorption property [J].Solid State Communications，
2014，218:50-55.
[18] 吴天斌，张鹏，马珺，等.超临界流体中制备微孔和介孔结
构金属有机框架负载 Ru 及其催化性能 [J]. 催化学报，
2013，34(1):167-175.
Wu T B，Zhang P，Ma J，et al.Catalytic activity of immobilized Ru nanoparticles in a porous metal-organic framework using supercritical fluid[J].Chinese Journal of Catalysis，2013，34(1):167-175.
[19] Masciocchi N，Bruni S，Cariati E，et al.Extended Polymorphism in Copper (II) Imidazolate Polymers:A Spectroscopic
and XRPD Structural Study[J].Inorganic Chemistry，2001，40
(23):5897-5905.
[20] Tabares L C，Navarro J A R，Salas J M.Cooperative Guest
Inclusion by a Zeolite Analogue Coordination Polymer.Sorption Behavior with Gases and Amine and Group 1 Metal
Salts[J].Journal of the American Chemical Society,2001,123
(3):383-387.
[21] Priyadarshini S，Joseph P J A，Kantam M，et al.Copper MOF:
scope and limitation in catalytic hydroxylation and nitration of aryl halides[J].Tetrahedron，2013，69(31):6409-6414.
[22] Wang Q M，Shen D M，Bulow M，et al.Metallo-organic molecular sieve for gas separation and purification[J].Microporous and Mesoporous Materials，2002，55(2):217-230
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