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Cyanosilylation of Aldehydes Catalyzed by Ag(I)- and Cu(II)-Arylhydrazone Coordination Polymers in Conventional and in Ionic Liquid Media

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Cyanosilylation of Aldehydes Catalyzed by Ag(I)- and Cu(II)-Arylhydrazone Coordination Polymers in Conventional and in Ionic Liquid Media catalysts Article Cyanosilylation of Aldehydes Catalyzed by Ag(I)- and Cu(II)-Arylhydrazone Coordination Polymers in Conventional and in Ionic Liquid Media Gonçalo A. O. Tiago 1, Kamran T. Mahmudov 1,2,*, M. Fátima C. Guedes da Silva 1,* , Ana P. C. Ribeiro 1,* , Luís C. Branco 3, Fedor I. Zubkov 4 and Armando J. L. Pombeiro 1 1 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049–001 Lisboa, Portugal; [email protected] (G.A.O.T.); [email protected] (A.J.L.P.) 2 Department of Chemistry, Baku State University, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan 3 LAQV-REQUINTE, Departamento de Química, Faculdade de Ciências e Tecnologias da Universidade Nova de Lisboa, Quinta da Torre, 2829-516 Caparica, Portugal; [email protected] 4 Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St., Moscow 117198, Russian; [email protected] * Correspondence: [email protected] or [email protected] (K.T.M.); [email protected] (M.F.C.G.d.S.); [email protected] (A.P.C.R.) Received: 22 February 2019; Accepted: 15 March 2019; Published: 20 March 2019 0 Abstract: The novel Ag(I) and Cu(II) coordination polymers [Ag(m3-1κO;2:3κO ;4κN-HL)]n·n/2H2O(1) − and [Cu(en)2(m-1κO;2κN-L)]n·nH2O(2) [HL = 2-(2-(1-cyano-2-oxopropylidene)hydrazinyl)benzene sulfonate] were synthesized and characterized by IR and ESI-MS spectroscopies, elemental and single crystal X-ray diffraction analyses. Compounds 1 and 2 as well as the already known complex salt [Cu(H2O)2(en)2](HL)2 (3) have been tested as homogenous catalysts for the cyanosilylation reaction of different aldehydes with trimethylsilyl cyanide, to provide cyanohydrin trimethylsilyl ethers. Coordination polymer 2 was found to be the most efficient one, with yields ranging from 76 to 88% in methanol, which increases up to 99% by addition of the ionic liquid [DHTMG][L-Lactate]. Keywords: Ag(I) and Cu(II) coordination polymers; arylhydrazone; catalysis; ionic liquids; cyanosilylation reaction 1. Introduction Cyanohydrins are industrially valuable substrates and important intermediates for the preparation of α-aminonitriles, α-hydroxyketones, α-hydroxyacids, β-hydroxyamines, and β-aminoalcohols, among others [1]. The main synthetic route for the synthesis of cyanohydrins is the catalytic addition of the cyano group to a carbonyl compounds. Trimethylsilyl cyanide (TMSCN) is a frequently explored substrate for catalytic cyanation reaction since it is easy to handle, it has a high atom economy without providing side reactions, and its Si–C bond has low dissociation energy (Scheme1) [ 2–7], therefore, contrasting with the toxic nature of other cyanide sources such as HCN, NaCN, KCN, etc. Numerous catalysts, including Lewis acids [8–10], Lewis bases [11–13], oxazaborolidinium ion [14,15], amino-thiourea [16,17], organic-inorganic salts [18–22], N-heterocyclic carbenes [23,24], nonionic bases [25,26], Ti,Al-phosphine oxide bifunctional species with carbohydrate or binaphthol scaffolds [27–29], Ti,Al-N-oxide bifunctional catalysts with proline, pyrrolidine and 1,2-diamino ligands [30–32], V-, Mn-, Al-, and Ti-salen complexes [33–36], chiral Ti-α,α,α,α-1,3-dioxolane-tetraaryl-4,5-dimethanols [37,38], Cu(II) and Co(II/III) hydrazone complexes [39,40] and also metal organic frameworks (MOFs) [41–44], have been developed for this transformation. According to the proposed reaction mechanism [1], the coordination or Catalysts 2019, 9, 284; doi:10.3390/catal9030284 www.mdpi.com/journal/catalysts Catalysts 2018, 8, x FOR PEER REVIEW 2 of 17 carbohydrate or binaphthol scaffolds [27–29], Ti,Al-N-oxide bifunctional catalysts with proline, pyrrolidine and 1,2-diamino ligands [30–32], V-, Mn-, Al-, and Ti-salen complexes [33–36], chiral Ti- α,α,α,α-1,3-dioxolane-tetraaryl-4,5-dimethanols [37,38], Cu(II) and Co(II/III) hydrazone complexes Catalysts 2019, 9, 284 2 of 16 [39,40] and also metal organic frameworks (MOFs) [41–44], have been developed for this transformation. According to the proposed reaction mechanism [1], the coordination or noncovalent noncovalentbond acceptor bond behavior acceptor of the behavior oxygen ofatom the of oxygen an aldehyde atom ofenhances an aldehyde the electrophilic enhances the character electrophilic of the charactercarbon atom of theat C=O, carbon which atom makes at C=O, it more which susceptible makes it moreto a nucleophilic susceptible attack to a nucleophilic by the cyano attack group. by theThus, cyano the reaction group. Thus,rate and the yield reaction of cyanohydrin rate and yield trimethylsilyl of cyanohydrin ethers trimethylsilyl are strongly ethers dependent are strongly on the dependentnature of metal on the center nature and of the metal coordinated center and ligand the coordinated in the metal ligand complex in thecatalyzed metal complexcyanation catalyzed reaction cyanation[1]. reaction [1]. Scheme 1. Cyanosilylation of aldehydes. MOFs or coordination polymers are attractive notnot only as storage, transporter, magnetic and luminescence materials [[45–48],45–48], but also as catalystscatalysts forfor variousvarious catalyticcatalytic transformations,transformations, such as alkane/alcohol oxidation oxidation [49,50], [49,50], C–C C–C bond bond format formationion [40,44], [40,44], etc., etc., from from the viewpoint of green chemistry. TheThe design design and and synthesis synthesis of coordination of coordination polymer polymer catalysts, catalysts, in particular in beingparticular inexpensive, being highlyinexpensive, efficient highly and efficient selective and with selective a wide with range a wide of range substrates, of substrates, remains remains a challenging a challenging goal goal in cyanosilylationin cyanosilylation reaction. reaction. Having Having this this objective objective in in mind, mind, we weintend intend toto reportreport thethe synthesissynthesis of new copper(II) andand Ag(I)Ag(I) coordinationcoordination polymers polymers bearing bearing an an arylhydrazone arylhydrazone ligand ligand and and their their application application in cyanosilylationin cyanosilylation reaction reaction of differentof different aldehydes aldehydes with with trimethylsilyl trimethylsilyl cyanide. cyanide. Moreover, ionic liquids (ILs) have wide applicationsapplications in catalysis, namely as green solvents or reaction promoters [[51],51], beingbeing able,able, in some cases, to enhance the reaction rate, improve the yield and selectivity in organic transformations under mild conditions. To To date, a few ILs have been reported in thethe cyanosilylationcyanosilylation of aldehydes [[52,53].52,53]. Thus, another aim of this work is to use a cooperativecooperative action of ILs and coordination polymers in cyanosilylation reaction, a type of approach that we have successfully applied in thethe oxidationoxidation ofof alkanesalkanes [[54,55]54,55] andand oxidationoxidation ofof alcoholsalcohols [[56].56]. 2. Results and Discussion 2.1. Synthesis and Characterization of 1–3 2.1. Synthesis and Characterization of 1–3 Sodium 2-(2-(1-cyano-2-oxopropylidene)hydrazinyl)benzenesulfonate (NaHL) and [Cu(H O) (en) ] Sodium 2-(2-(1-cyano-2-oxopropylidene)hydrazinyl)benzenesulfonate (NaHL)2 2 and2 (HL)2 (3) were synthesized as previously reported [57]. Reaction of AgNO3 or Cu(NO3)2·2.5H2O with [Cu(H2O)2(en)2](HL)2 (3) were synthesized as previously reported [57]. Reaction of AgNO3 or NaHL in methanol in the presence of nitric acid or ethylenediamine (en) led to the novel coordination Cu(NO3)2∙2.5H2O with NaHL0 in methanol in the presence of nitric acid or ethylenediamine (en) led polymer [Ag(µ3-1κO;2:3κO ;4κN-HL)]n·n/2H2O(1) or [Cu(en)2(µ-1κO;2κN-L)]n·nH2O(2), respectively to the novel coordination polymer [Ag(μ3-1κO;2:3κO’;4κN-HL)]n∙n/2H2O (1) or [Cu(en)2(μ-1κO;2κN- (Scheme2). Both polymers were characterized by IR spectroscopy, ESI-MS, elemental analysis, and single L)]n∙nH2O (2), respectively (Scheme 2). Both polymers were characterized by IR spectroscopy, ESI- crystal X-ray diffraction. MS, elemental analysis, and single crystal X-ray diffraction. Catalysts 2019, 9, 284 3 of 16 Catalysts 2018, 8, x FOR PEER REVIEW 3 of 17 Scheme 2. Synthesis of 1–3. Hydrate water molecules were omitted in 1 and 2. Scheme 2. Synthesis of 1–3. Hydrate water molecules were omitted in 1 and 2. The IR spectra of 1 and 2 (see experimental section) show the expected N≡C, C=O and C=N ≡ vibrationsThe which IR spectra generally of 1 and occur 2 (see at experimental wavenumbers section) different show from the expected those of N theC, proligandC=O and C=N (i.e., 2206, 1645,vibrations and average which 1570 generally cm−1 occur, respectively at wavenumbers [57]), therefore different attesting from those the of involvement the proligand of (i.e., the 2206, compound 1645, and average 1570 cm−1, respectively [57]), therefore attesting the involvement of the compound in coordination to the metals. The nitrile group stretching frequency n(C≡N) in 1 is 8 cm−1 above that ≡ −1 in coordination to the metals. The nitrile group stretching frequency ν(C N) in 1 is 8 cm above that−1 measured for NaHL which is consistent with its coordination. In 2, that frequency is− 2 cm below. measured for NaHL which is consistent with its coordination. In 2, that frequency is 2 cm 1 below. −1 ConcerningConcerning the the ketone ketone vibrations,vibrations, νn(C=O),(C=O), they they occur occur 16 (for 16 1 (for) and1) 30 and (for 30 2) (forcm−1 2above) cm thoseabove of the those of −1 theNaHL NaHL reference reference value, value, whereas whereas ν(C=N)n(C=N) assume assume values 13 values (for 1) 13and (for 26 (for1) and 2) cm 26−1 (forabove2 )the cm averageabove the averageone for one NaHL. for NaHL.
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