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Molecules 2019, 24, 182 Molecules 2019, 24, x FOR PEER REVIEW 24 of 41 232 24 of 42 Molecules 2019, 24, x FOR PEER REVIEW Cs2CO3,,ii()iii)nisnesretriotinonofoCf COO2 initnotoSiS−iH−,Hii,i)(ifioi)rmfoyrmlaytiloantionf aomf ainmeisnbesybsyilyslilfyolrfmoramtea,taen, adnidv)(irve)druecdtuiocntionf 24 of 42 Cs2CO3, ii) insertion of CO2 into Si−H, iii) formylation of amines by silyl formate, and iv) reduction of fofrfmoramaidmeisdteos mtoemtheytlhaymlainmeisn.es. formamides to methylamines. Scheme25.Cs2CO3cattallysiisfforrsellecttiiveN--fforrmyllattiion//NN-m-metehthyylalatitoionnaannddpproroppooseseddmeecchhaannisism.. 23 Scheme 25. Cs2CO3 catalysis for selective N-formylation/N-methylation and proposed mechanism. In2007,theHegroupdevelopedaglycinebetaine-catalyzedstrategyforthereactionofCO with In 2007, the He group developed a glycine betaine-catalyzed strategy for the reaction o2f CO2 In 2007, the He group developed a glycine betaine-catalyzed strategy for the reaction of CO2 aminesanddiphenylsilane(Scheme26a)[125].ThroughtuningtheamountofCO andthereaction with amines and diphenylsilane (Scheme 26a) [125]. Through tuning the amoun2t of CO2 and the with amines and diphenylsilane (Scheme 26a) [125]. Through tuning the amount of CO2 and the temperature, three kinds of products, i.e., formamide, methylamine, and aminal, were successively reaction temperature, three kinds of products, i.e., formamide, methylamine, and aminal, were reaction temperature, three kinds of products, i.e., formamide, methylamine, and aminal, were obtained.ThisschemefirstlyachievedthehierarchicalreductionofCO withamineandhydrosilane successively obtained. This scheme firstly achieved the hierarchical r2eduction of CO2 with amine successively obtained. This scheme firstly achieved the hierarchical reduction of CO2 with amine using organocatalysis with wide substrate scope. Almost at the same time, the Han group also and hydrosilane using organocatalysis with wide substrate scope. Almost at the same time, the Han and hydrosilane using organocatalysis with wide substrate scope. Almost at the same time, the Han reportedtheglycinebetaine-catalyzedtransformationofCO withaminestosynthesizeN-substituted group also reported the glycine betaine-catalyzed transform2 ation of CO2 with amines to synthesize group also reported the glycine betaine-catalyzed transformation of CO2 with amines to synthesize compounds (Scheme 26b) [126]. Similarly, the selectivity to the reductive products could be controlled N-substituted compounds (Scheme 26b) [126]. Similarly, the selectivity to the reductive products N-substituted compounds (Scheme 26b) [126]. Similarly, the selectivity to the reductive products by the molar ratio of reactants (i.e., CO , amines, and PhSiH ) and the temperature. Subsequently, could be controlled by the molar rat2io of reactants (i.e., 3CO2, amines, and PhSiH3) and the could be controlled by the molar ratio of reactants (i.e., CO2, amines, and PhSiH3) and the they used lecithin as an organocatalyst for the formylation and methylation of various amines with temperature. Subsequently, they used lecithin as an organocatalyst for the formylation and temperature. Subsequently, they used lecithin as an organocatalyst for the formylation and CO tocorrespondingformamidesandmethylaminesviausingPhSiH asthehydrogensource[127]. met2hylation of various amines with CO2 to corresponding formamides3 and methylamines via using methylation of various amines with CO2 to corresponding formamides and methylamines via using Meanwhile, the product selectivity could also be easily controlled by the molar ratio of reactants and PhSiH3 as the hydrogen source [127]. Meanwhile, the product selectivity could also be easily PhSiH3 as the hydrogen source [127]. Meanwhile, the product selectivity could also be easily reaction temperature. controlled by the molar ratio of reactants and reaction temperature. controlled by the molar ratio of reactants and reaction temperature. R1 H R1N H N+ - 1 O R1 Me R1 R1 N+CO2+RxSiHy 2 +CO+RSiH N R1 NH+ 2 + 2 2 Cat. Cat. O N+ O O formamide methylamine a) Reaction conditions in He group: o aminal a) Reaction conditions in He group: N-Formylation:Cat.(10mol%),PhSiH (2equiv),50 C,1MPaCO,18h; 22o2 N-Formylation:Cat.(10mol%),PhSiH (2equiv),50 C,1MPaCO,18h; 22 o2 O- R1 R1N Me R1N O RNH+ N + NN R22xy R2R2R2R2 R R2RRR N-Methylation:Cat.(5mol%),PhSiH (4equiv),CHCN(2mL),70 C,0.1MPaCO,12h; 223o2 N-Methylation:Cat.(5mol%),PhSiH (4equiv),CHCN(2mL),70 C,0.1MPaCO,12h; 223o2 Aminal formation: Cat. (10 mol%), Ph SiH (3 equiv), 50 C, CO (1 equiv), 4 h. 22o2 Aminalformation:Cat.(10mol%),Ph2SiH2(3equiv),50 C,CO2(1equiv),4h. b) Reaction conditions in Han group: b) Reaction conditions in Han group: o N-Formylation:Cat.(3mol%),PhSiH (2equiv),CHCN(1mL),25 C,0.5MPaCO,4-12h; 33o2 N-Formylation:Cat.(3mol%),PhSiH (2equiv),CHCN(1mL),25 C,0.5MPaCO,4-12h; 33o2 N-Methylation: Cat. (5 mol%), PhSiH (4 equiv), CH CN (1 mL), 100 C, 0.3 MPa CO , 6 h; 33o2 N-Methylation: Cat. (5 mol%), PhSiH (4 equiv), CH CN (1 mL), 100 C, 0.3 MPa CO , 6 h; 33o2 Aminalformation:Cat.(1.5mol%),PhSiH (2equiv),CHCN(1mL),100 C,0.2MPaCO,4h. 33o2 Aminalformation:Cat.(1.5mol%),PhSiH3(2equiv),CH3CN(1mL),100 C,0.2MPaCO2,4h. Scheme 26. Glycine betaine-catalyzed selective N-formylation/N-methylation. Scheme 26. Glycine betaine-catalyzed selective N-formylation/N-methylation. formamide methylamine aminal Scheme 26. Glycine betaine-catalyzed selective N-formylation/N-methylation. Recently, Chen and Xia reported an efficient DBU catalytic system for the selective N-methylation Recently, Chen and Xia reported an efficient DBU catalytic system for the selective Recently, Chen and Xia reported an efficient DBU catalytic system for the selective andN-formylationofamineswithCO andPMHS(Scheme27)[128].TheN-methylationproductsin 2 N-methylation and N-formylation of amines with CO2 and PMHS (Scheme 27) [128]. The N-methylation and N-formylation of amines with CO2 and PMHS (Scheme 27) [128]. The N-methylation products in high yields are obtained with 1 mol% DBU at 100 °C, and selective N-methylation products in high yields are obtained with 1 mol% DBU at 100 °C, and selective N-formylation of amines is realized with 10 mol% DBU at a lower temperature. N-formylation of amines is realized with 10 mol% DBU at a lower temperature.PDF Image | Catalytic Conversion of Carbon Dioxide through C-N Bond
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