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Molecules 2019, 24, x FOR PEER REVIEW 5 of 42 Molecules 2019, 24, 182 5 of 41 In 2014, He and co-workers reported that silver complex [(PPh3)2Ag]2CO3, which could be formed in situ from Ag2CO3 and PPh3, promoted the reaction even under atmospheric CO2 pressure [32]. According to the results of 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, CO2 In 2014, He and co-workers reported that silver complex [(PPh3)2Ag]2CO3, which could be formed and propargylic alcohol were presumably simultaneously activated by [(PPh3)2Ag]2CO3, which in situ from Ag2CO3 and PPh3, promoted the reaction even under atmospheric CO2 pressure [32]. greatly facilitated the reac1tion (Fi1g3ure 2). Additionally, the scope of the reaction system was According to the results of H and C nuclear magnetic resonance (NMR) spectroscopy, CO2 and demonstrated to be wide (Figure 3). Furthermore, the combinations of Ag2WO4 and Ag2O with PPh3, propargylic alcohol were presumably simultaneously activated by [(PPh3)2Ag]2CO3, which greatly respectively, were also used as catalysts to synthetize β-oxopropylcarbamates under mild reaction facilitated the reaction (Figure 2). Additionally, the scope of the reaction system was demonstrated conditions. Ag2WO4/PPh3 showed good catalytic activity under the solvent-free condition primarily to be wide (Figure 3). Furthermore, the combinations of Ag2WO4 and Ag2O with PPh3, respectively, because of the reactant activation through [Ag(PPh3)]+ and [WO4]2− (Scheme 3a) [21]. Nevertheless, were also used as catalysts to synthetize β-oxopropylcarbamates under mild reaction conditions. the aromatic amines could not afford the desired products in this system. In contrast, the Ag2WO4/PPh3 showed good catalytic activity under the solvent-free condition primarily because of employment of Ag2O/PPh3 successfully+accomplish2e−d the reaction of propargylic alcohols and the reactant activation through [Ag(PPh3)] and [WO4] (Scheme 3a) [21]. Nevertheless, the aromatic ammonium carbamate (amine-CO2) to achieve the quantitative fixation of CO2 [33]. Herein, amines could not afford the desired products in this system. In contrast, the employment of Ag2O/PPh3 ammonium carbamate formed from amine and CO2 was used as a CO2 surrogate. As shown in successfully accomplished the reaction of propargylic alcohols and ammonium carbamate (amine-CO2) Scheme 4, propargylic carbonate intermediate A is initially generated from the reaction of to achieve the quantitative fixation of CO2 [33]. Herein, ammonium carbamate formed from amine propargylic alcohol with ammonium carbamate. Subsequently, the intermediate A is converted into and CO2 was used as a CO2 surrogate. As shown in Scheme 4, propargylic carbonate intermediate A is silver propargylic carbonate B in presence of silver(I) catalyst. Then, after the activation of C≡C bond initially generated from the reaction of propargylic alcohol with ammonium carbamate. Subsequently, by the silver species, intermediate C is obtained and follows by the formation of α-alkylidene cyclic the intermediate A is converted into silver propargylic carbonate B in presence of silver(I) catalyst. carbonate. Finally, in the presence of a secondary amine, the corresponding β-oxopropylcarbamate Then, after the activation of C≡C bond by the silver species, intermediate C is obtained and follows can be obtained via tautomerization. by the formation of α-alkylidene cyclic carbonate. Finally, in the presence of a secondary amine, the corresponding β-oxopropylcarbamate can be obtained via tautomerization. Table 1. Silver-containing catalytic systems. Catalyst(catalyticamount/mol%)TableS1o.lSveilnvter-contaTi/n°CingcatalyPt/iMcPsyastems.t/h Yield/%a Ref. Ag2CO3 (1.5), PPh3 (6) CH3CN 30 0.1 16 68-98 [32] Ref. [21] [33] Catalyst (catalytic amount/mol%) Solvent T/◦C P/MPa t/h Yield/% a Ag2WO4 (1), PPh3 (2) - 50 0.5 12 30-97 0.1 16 68–98 b - 18 37-96 0.5 12 30–97 Ag2CO3 (1.5), PPh3 (6) CH3CN 30 [32] Ag2O (2), PPh3 (8) CH3CN 60 Ag2WO4 (1), PPh3 (2) Ag2CO3 (0.01), (p-MeOC6H4)3P Ag O (2), PPh (8) - 50 CH CN 60 - 18 37–96 b [21] c [33] [34] (0.04) c bb 2 3 CHCl3 325 2 96 30.5-93.2 [34] [35] [35] Ag2CO3 (0.01), (p-MeOC6H4)3P (0.04) AgCl (5)A, EgtC4Nl (C5)l,(E9)t4NCl (9) CH3CN CHCl3 25 CH3CN60 60 2 96 0.10.1 2244 30.5–93.2 29–298-98 aa bb c IsoIlsaotleadtedyiyeiledld;;NNMRRyiield; gaschrroomataotgorgarpahpyh(yGC(G)Cyi)elydi.eld. (a) (b) (c) C2 (d) (e) (f) * C1 C3 1 13 Figure 2. 1 H-NMR (a,b) and13 C-NMR (c–f) investigation. (a,b) 2-Methyl-4-phenylbut-3-yn-2-ol Figure 2. H-NMR (a, b) and C-NMR (c–f) investigation. (a,b) 2-Methyl-4-phenylbut-3-yn-2-ol (8.0 (8.0 mg), Ag2CO3 (2.8 mg) and Ph3P (10.5 mg) ([D6] DMSO 0.6 mL). (c,d) 2-methylbut-3-yn-2-ol mg), Ag2CO3 (2.8 mg) and Ph3P (10.5 mg) ([D6] DMSO 0.6 mL). (c,d) 2-methylbut-3-yn-2-ol (20.2 mg), (20.2 mg), AgNO3 (40.8 mg) (CDCl3 0.6 mL). (e) [(Ph3P)2Ag]2CO3 (158.6 mg) in 0.6 mL of CDCl3. AgNO3 (40.8 mg) (CDCl3 0.6 mL). (e) [(Ph3P)2Ag]2CO3 (158.6 mg) in 0.6 mL of CDCl3. (f) (f) [(Ph P) Ag] CO (158.6 mg) in 0.6 mL of CDCl in the presence of 13CO (0.1 MPa). Reprinted with 3223 3 132 [(Ph3P)2Ag]2CO3 (158.6 mg) in 0.6 mL of CDCl3 in the presence of CO2 (0.1 MPa). Reprinted with permission from [32] (Copyright 2014 John Wiley and Sons). permission from [32] (Copyright 2014 John Wiley and Sons).PDF Image | Catalytic Conversion of Carbon Dioxide through C-N Bond
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