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Molecules 2019, 24, 182 7 of 41 2.2. Direct Carboxylation/Cyclization with C-N Bond Formation Molecules 2019, 24, x FOR PEER REVIEW 7 of 42 2.2.1. Carboxylative Cyclization of Propargyl Amines with Carbon Dioxide 2.2.1. Carboxylative Cyclization of Propargyl Amines with Carbon Dioxide PropParogpyalircgaymlicinaems,inaesss,oamsesomfteheofimthpeorimtapnotrptarnotpaprgoyplaircgcyolimcpcomunpdosu,nadrse,naoretonoltyoenalsyilyeasvilayilable but aalsvoaislaubilteabulet afolsrofsuritahbelre tforarnfusrftohremr tartainosnfosrbmeactaiounsseboefcatuhseeiroftwthoeirfutwncotfiuoncatliosnitaelsi(teasn(anmaimnoingoroup group and a triple bond) [36]. To date, great efforts have been made to develop the carboxylative and a triple bond) [36]. To date, great efforts have been made to develop the carboxylative cyclization cyclization of propargylic amines with CO2 to obtain 2-oxazolidinones. As described in Scheme 5, of propargylic amines with CO2 to obtain 2-oxazolidinones. As described in Scheme 5, CO2 initially CO2 initially reacts with propargylic amine to afford intermediate A. Then, an intramolecular reacts with propargylic amine to afford intermediate A. Then, an intramolecular cyclization occurs with cyclization occurs with the generation of product. Notably, the second step is considered to be the the generation of product. Notably, the second step is considered to be the rate-determining step [37]. rate-determining step [37]. Scheme 5. The mechanism for carboxylative cyclization of propargylic amines with CO2. Scheme 5. The mechanism for carboxylative cyclization of propargylic amines with CO2. Taking into account that activation of the carbon-carbon triple bond is of importance to promote Taking into account that activation of the carbon-carbon triple bond is of importance to the carboxylative cyclization, coinage metals (Au, Ag and Cu) have been extensively employed as promote the carboxylative cyclization, coinage metals (Au, Ag and Cu) have been extensively catalysts due to π-coordination with the alkyne (Scheme 6). Among them, N-heterocyclic carbene employed as catalysts due to π-coordination with the alkyne (Scheme 6). Among them, (NHCN)-hAeutercoocmycpliclecxaerbseonbev(NioHuCsl)y-ApuacvoemdptlhexeeswoabyvitousclhyepmaviceadlthfiexwataioyntoocfheCmOica(l1fixaantdion2,ofSCchOe2m(1e 6a). 2 Origiannadlly2, SIckhaermiyea6ae)t. Oalr.iginfoaullyn,dIktahriayta AetuaCl.lf(oIPunr)d (t1h)atwAausClc(aIPpra)b(1le) woafsccatpaalyblzeinogf cathtaelyszyingththeesis of synthesis of (Z)-5-alkylidene-1,3-oxazolidin-2-ones in methanol under mild conditions [38]. Further (Z)-5-alkylidene-1,3-oxazolidin-2-ones in methanol under mild conditions [38]. Further investigation investigation of the substrate scope revealed that the catalytic activity was weakened by the of the substrate scope revealed that the catalytic activity was weakened by the introduction of aromatic introduction of aromatic substituents at the alkyne terminus [39]. Metallodendrimers have a kind of substituents at the alkyne terminus [39]. Metallodendrimers have a kind of functional or catalytic site functional or catalytic site at the core, and their solubility and physical properties can be modified at the core, and their solubility and physical properties can be modified via peripheral structures [40]. via peripheral structures [40]. Accordingly, amphiphilic dendritic Au/G1[PEG] (2) also exhibited Accordingly, amphiphilic dendritic Au/G1[PEG] (2) also exhibited good catalytic activity in aqueous good catalytic activity in aqueous media under atmospheric pressure of CO2 [41]. media under atmospheric pressure of CO2 [41]. Moreover, Sadeghzadeh developed various fibrous nanosilica (KCC-1)/metal nanoparticles Moreover, Sadeghzadeh developed various fibrous nanosilica (KCC-1)/metal nanoparticles (NPs) (NPs) to catalyze the incorporation of CO2 into propargylic amines (3, 4 and 5, Scheme 6a). KCC-1 tocathaalsyazeunthiqeueinficborropuosrmatoiropnholfogCyObeairnintogwpritohphairgghysluicrfacmeianreas,(t3u,na4balenpdor5e,sSizceheamndep6oare).voKluCmCe-,1has 2 a unicqounetrfiolblarboluespamrtoicrlpehsiozleo,gayndbiemaprirnogvewdisthabhiligtyh. Hsuigrhfapcoelyagrleyac,ertouln(aHbPlGe)p@oKrCeCs-i1z/ePPahn2d/Apuo(r3e) avnodlume, Fe3O4/KCC-1/tetrazolylidene/Au (4) catalyst not only catalyzed and gave 2-oxazolidinones in good controllable particle size, and improved stability. High polyglycerol (HPG)@KCC-1/PPh2/Au (3) and to excellent yields under 0.5 MPa CO2 pressure at room temperature with water as solvent, but also Fe3O4/KCC-1/tetrazolylidene/Au (4) catalyst not only catalyzed and gave 2-oxazolidinones in good could be recovered and reused several times without appreciable loss of activity [42,43]. Especially, to excellent yields under 0.5 MPa CO2 pressure at room temperature with water as solvent, but also the turnover number of the latter system was up to 1200. In addition, KCC-1/Salen/Ru(II) NPs (5) could be recovered and reused several times without appreciable loss of activity [42,43]. Especially, the was also efficient in production of oxazolidinones, but high reaction temperature was required [44]. turnover number of the latter system was up to 1200. In addition, KCC-1/Salen/Ru(II) NPs (5) was Recently, a gold catalyst containing an Z-type ligand composed of a diphosphine-borane (DPB), also efficient in production of oxazolidinones, but high reaction temperature was required [44]. namely [Au(DPBF)]SbF6 (6, Scheme 6a) for the carboxylation reaction was developed [45]. The Recently, a gold catalyst containing an Z-type ligand composed of a diphosphine-borane (DPB), desired products were formed in air (ca. CO2 300–700 ppm) at room temperature in the presence of F name1l,y8-d[Aiauza(DbicPyBclo)[]5S.b4.F0]u(n6d,eSc-c7h-enmee(D6BaU))f.oHrotwhevcear,rtbhoexyyielaldtisoonftrheavcatisotnmawjoarsitydoefvceolrorpesepdon[4d5in].g The 6 desirepdropdruocdtsuwcetsrewaeroreunfodr4m0%ed. in air (ca. CO2 300–700 ppm) at room temperature in the presence of As shown in Scheme 6b, silver compounds also displayed excellent performance in the 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). However, the yields of the vast majority of corresponding carboxylative cyclization. In 2012, Yoshida et al. reported that AgNO3/DBU (7) catalytic system was products were around 40%. used for CO2 capture and transformation at 60 °C and 0.1 MPa CO2 in dimethyl sulfoxide (DMSO) As shown in Scheme 6b, silver compounds also displayed excellent performance in the [46]. During the process, atmospheric CO2 was initially trapped by DBU to give DBU-CO2 complex carboxylative cyclization. In 2012, Yoshida et al. reported that AgNO3/DBU (7) catalytic system subsequently, which could propel the reaction. ◦ was used for CO2 capture and transformation at 60 C and 0.1 MPa CO2 in dimethyl sulfoxide Additionally, a simple and low cost CuI/DBU (8, Scheme 6c) system was explored to synthesize (DMSO) [46]. During the process, atmospheric CO2 was initially trapped by DBU to give DBU-CO2 2-oxazolidinones through the coupling reaction of propargylic amines and CO2 by Wang et al. [47]. complex subsequently, which could propel the reaction. The DFT results suggested that CuI and DBU have an excellent synergistic effect in promoting the Aredacdtitoinosn.aDllByU, acosiumldpclaepatnurdelaonwd tcroasntsfCeur pI/roDtoBnUs;(m8,eSanchwehmile,6Ccu)Isaycsttivematewd tahseeCx≡pClotreipdletobosnydntohfesize 2-oxazolidinones through the coupling reaction of propargylic amines and CO2 by Wang et al. [47]. The DFT results suggested that CuI and DBU have an excellent synergistic effect in promoting thePDF Image | Catalytic Conversion of Carbon Dioxide through C-N Bond
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