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Molecules 2019, 24, 182 26 of 41 Molecules 2019, 24, x FOR PEER REVIEW 26 of 42 Scheme 29. DBU-catalyzed selective N-methylation/N-formylation and possible mechanism [130]. Scheme 29. DBU-catalyzed selective N-methylation/N-formylation and possible mechanism [130]. Initially, the coordination of copper with phosphine ligand Ph CyP or DPPB led to the copper 2 Initially, the coordination of copper with phosphine ligand Ph2CyP or DPPB led to the copper complexandthesubsequentformationoftheactiveCu–Hspecies,followedbyCO insertionwiththe 2 complex and the subsequent formation of the active Cu–H species, followed by CO2 insertion with generation of the copper formate (Cycle I). Then, copper formate reacts with amine and hydrosilane the generation of the copper formate (Cycle I). Then, copper formate reacts with amine and to give the formamide along with the formation of the active Cu–H species (Cycle II). The catalytic hydrosilane to give the formamide along with the formation of the active Cu–H species (Cycle II). ability of copper complex determines the final products through the catalytic cycle I or cycle II. The catalytic ability of copper complex determines the final products through the catalytic cycle I or The Cu(Ph CyP) complex gave the final formamide product, and Cu(DPPB) could further catalyze the 2 cycle II. The Cu(Ph2CyP) complex gave the final formamide product, and Cu(DPPB) could further formamide reduction to the methylamine product. catalyze the formamide reduction to the methylamine product. The Mechanism of Metal and Organocatalysis The Mechanism of Metal and Organocatalysis The previously proposed catalytic pathways for the reactions of N-methylation and N-formylation The previously proposed catalytic pathways for the reactions of N-methylation and are summarized in Scheme 30 [131]. Among, the mechanisms for the synthesis of aminal from amine, N-formylation are summarized in Scheme 30 [131]. Among, the mechanisms for the synthesis of CO2 and hydrosilane (Cantat’s TBD-catalyzed method) is similar to the methylation (Scheme 31) [132]. aminal from amine, CO2 and hydrosilane (Cantat’s TBD-catalyzed method) is similar to the The aminal product is obtained via a [Si]OCH2O[Si] intermediate, and HC(=O)O[Si] intermediate does methylation (Scheme 31) [132]. The aminal product is obtained via a [Si]OCH2O[Si] intermediate, not react with amine to form formamide. Therefore, the formation of aminal does not undergo the and HC(=O)O[Si] intermediate does not react with amine to form formamide. Therefore, the formamide intermediate process. Besides, other organocatalysts including glycine betaine [125,126], formation of aminal does not undergo the formamide intermediate process. Besides, other DBU [128], K2WO4 [129], also supported the mechanism of aminal intermediate for the methylation of organocatalysts including glycine betaine [125,126], DBU [128], K2WO4 [129], also supported the amines with CO2 using hydrosilane as reductant through detailed control experiments (Scheme 32, mechanism of aminal intermediate for the methylation of amines with CO2 using hydrosilane as equations 1–3) and DFT study [133]. In addition, in some metal-based systems such as Fe [120], reductant through detailed control experiments (Scheme 32, equations 1–3) and DFT study [133]. In Cs [124], Cu [130], and a few organocatalysts (e.g., TBAF [123], lecithin [127], etc.), the experimental addition, in some metal-based systems such as Fe [120], Cs [124], Cu [130], and a few organocatalysts evidence supports the mechanism of further formamide hydrogenation to the corresponding the (e.g., TBAF [123], lecithin [127], etc.), the experimental evidence supports the mechanism of further methylation under the corresponding conditions (Scheme 32, equations 4–8). In these works, control formamide hydrogenation to the corresponding the methylation under the corresponding experiments, e.g., using the product formamide as reaction material, were carried out to demonstrate conditions (Scheme 32, equations 4–8). In these works, control experiments, e.g. using the product the pathway (Scheme 30). formamide as reaction material, were carried out to demonstrate the pathway (Scheme 30).PDF Image | Catalytic Conversion of Carbon Dioxide through C-N Bond
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