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Molecules 2019, 24, x FOR PEER REVIEW 9 of 42 Scheme 6. A summary of coinage metals catalysts in carboxylative cyclization of propargylic amines with CO2. Molecules 2019, 24, 182 9 of 41 In recent years, considerable attention has also been paid to Zn-based catalysts in CO2 fixation because of their tunable Lewis acidity, natural abundance and eco-friendly properties. In 2016, He et In recent years, considerable attention has also been paid to Zn-based catalysts in CO2 fixation al. found that the mononuclear ZnII complex ZnCl2(TBD)2 (TBD = 1,5,7-triazabicyclo[4.4.0]dec-5-ene) because of their tunable Lewis acidity, natural abundance and eco-friendly properties. In 2016, He et al. II could fix CO2 by propargylic amines to deliver corresponding 2-oxazolidinones without any solvent found that the mononuclear Zn complex ZnCl2(TBD)2 (TBD = 1,5,7-triazabicyclo[4.4.0]dec-5-ene) (Scheme 7a) [50]. Nevertheless, the internal propargylic amine was unreactive with CO2 in this could fix CO2 by propargylic amines to deliver corresponding 2-oxazolidinones without any solvent catalytic system. In contrast, the terminal and internal secondary propargylamines were smoothly (Scheme 7a) [50]. Nevertheless, the internal propargylic amine was unreactive with CO2 in this catalytic transformed into oxazolidinone derivatives by Indenediide-based Pd complex catalysts under mild system. In contrast, the terminal and internal secondary propargylamines were smoothly transformed conditions in DMSO (Scheme 7b) [51]. In particular, six-membered cyclic carbamates and N-aryl into oxazolidinone derivatives by Indenediide-based Pd complex catalysts under mild conditions in oxazolidinones were obtained (Scheme 7c). In addition, primary propargylamines, which were DMSO (Scheme 7b) [51]. In particular, six-membered cyclic carbamates and N-aryl oxazolidinones prone to occurring side reaction due to the NH2 group, also led to the desired oxazolidinones in were obtained (Scheme 7c). In addition, primary propargylamines, which were prone to occurring good yields. side reaction due to the NH2 group, also led to the desired oxazolidinones in good yields. Scheme 7. Synthesis of 2-oxazolidinones via Zn- and Pd-catalyzed reaction. Scheme 7. Synthesis of 2-oxazolidinones via Zn- and Pd-catalyzed reaction. As can be seen from the above examples, the reported metal catalytic systems generally As can be seen from the above examples, the reported metal catalytic systems generally employed expensive noble metals or complicated catalytic components. At the same time, metal-free employed expensive noble metals or complicated catalytic components. At the same time, metal-free catalytic processes can reduce the cost and avoid the pollution caused by metals. In recent years, catalytic processes can reduce the cost and avoid the pollution caused by metals. In recent years, there are well-established protocols with vigorous metal-free catalytic systems such as TBA2[WO4] there are well-established protocols with vigorous metal-free catalytic systems such as TBA2[WO4] (TBA = tetra-n-butylammonium) [52], ILs [53], NHCs (e.g., 1,3-di-t-butylimidazol-2-ylidene) [54] (TBA = tetra-n-butylammonium) [52], ILs [53], NHCs (e.g., 1,3-di-t-butylimidazol-2-ylidene) [54] Bu4NF [55,56] and so on. Bu4NF [55,56] and so on. In 2012, Minakata reported an effective catalytic system being composed of t-BuOI and In 2012, Minakata reported an effective catalytic system being composed of t-BuOI and CH3CN CH3CN for the carboxylative cyclization of propargyl amine and CO2, and 2-oxazolidinone bearing for the carboxylative cyclization of propargyl amine and CO2, and 2-oxazolidinone bearing iodomethyl group could be generated under mild conditions (Scheme 8a) [57]. Afterwards, with iodomethyl group could be generated under mild conditions (Scheme 8a) [57]. Afterwards, with two two equivalents of a protic ionic liquid namely 1,8-diazabicyclo-[5.4.0]-7-undecenium 2-methyl- equivalents of a protic ionic liquid namely 1,8-diazabicyclo-[5.4.0]-7-undecenium 2-methyl- imidazolide ([DBUH][MIm]), the desired products were obtained in good to excellent yields imidazolide ([DBUH][MIm]), the desired products were obtained in good to excellent yields (Scheme 8b) [37]. Gratifyingly, this cheaper and greener catalyst could be easily recycled and reused (Scheme 8b) [37]. Gratifyingly, this cheaper and greener catalyst could be easily recycled and reused at least five times. Han et al. also found that [DBUH][MIm] promoted both the CO2 electrophilic at least five times. Han et al. also found that [DBUH][MIm] promoted both the CO2 electrophilic attack and the intramolecular cyclization step by capturing and transferring proton through theoretical attack and the intramolecular cyclization step by capturing and transferring proton through studies, respectively. theoretical studies, respectively. Very recently, the reaction of propargylic amines and CO2 were carried out in the presence Very recently, the reaction of propargylic amines and CO2 were carried out in the presence of a of a cyanuric acid (H3 CYA)-based organocatalyst (Scheme 8c) [58]. [Et4 N]3 [CYA] was the main cyanuric acid (H3CYA)-based organocatalyst (Scheme 8c) [58]. [Et4N]3[CYA] was the main component of the most effective catalyst among these organocatalysts. Notably, this was the first component of the most effective catalyst among these organocatalysts. Notably, this was the first reported example of direct organocatalytic conversion of low-concentration CO2 in air (0.04% v/v) reported example of direct organocatalytic conversion of low-concentration CO2 in air (0.04% v/v) for for 2-oxazolidinone synthesis. It could be ascribed to the better activation of CO2 in the presence of [H3-nCYA]nā (n = 1ā3) than that of [Phth]ā and [2-PyO]ā anions (Scheme 8e). Besides, triethanolaminePDF Image | Catalytic Conversion of Carbon Dioxide through C-N Bond
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