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Molecules 2019, 24, x FOR PEER REVIEW 21 of 42 Molecules 2019, 24, x FOR PEER REVIEW 21 of 42 As seen from Scheme 20a, Zhao et al. developed a three-component reaction of unsymmetrical As seen from Scheme 20a, Zhao et al. developed a three-component reaction of unsymmetrical allylic chlorides, CO2 and amines to afford allyl carbamates by Pd catalysis [109]. This method allylic chlorides, CO2 and amines to afford allyl carbamates by Pd catalysis [109]. This method tolerated various allyl carbamates in moderate yields but with excellent regioselectivity (99/1). tolerated various allyl carbamates in moderate yields but with excellent regioselectivity (99/1). Molecules 2019, 24, 182 21 of 41 A facile and efficient methodology for the synthesis of new acetal-type O-allyl carbamates by A facile and efficient methodology for the synthesis of new acetal-type O-allyl carbamates by regioselective coupling reaction of CO2, amines and aryloxyallenes was explored in 2018 (Scheme regioselective coupling reaction of CO2, amines and aryloxyallenes was explored in 2018 (Scheme (2S0cbh)e[m11e0]2.0Ab)w[1id10e]r. aAngweidofedreasnigredopf droedsiurcetds pwreordeuocbtstawinerde ionbmtaiondeedraintemtooedxecrealtlentot yeixecledlsleunstinygietlhdes 20b) [110]. A wide range of desired products were obtained in moderate to excellent yields using the ucastianlgytihcesycasteamlytoicf sAygsOteAmcoafnAdgTOBADc. JainandgTeBtDa.l.Jfiaonugndetthala.t faoucantdiotnhiactsapeccaiteisongiecnsepraetceiedsfgroemnerAagte(Id) catalytic system of AgOAc and TBD. Jiang et al. found that a cationic species generated from Ag(I) fsraoltmanAdg(TI)BsDalwt ansdthTeBkDeywascttihve kceoymapclteivxeincotmheptleraxnisnfothrme tartaionns,fowrmhiacthiown,aws ihnidchicawteads ibnydi1cHa-tNedMbRy salt and TBD was the key active complex in the transformation, which was indicated by 1H-NMR 1 sHtu-dNieMs.R studies. studies. Scheme 20. Synthesis of allyl carbamates from amines and CO2. Scheme 20. Synthesis of allyl carbamates from amines and CO2. Scheme 20. Synthesis of allyl carbamates from amines and CO2. 3.C-NBondFormationthroughCO Hydrogenation 3. C-N Bond Formation through CO2 Hydrogenation 3. C-N Bond Formation through CO2 Hydrogenation For the past fifteen years, reductive methylation using N-site-based nucleophiles and CO to For the past fifteen years, reductive methylation using N-site-based nucleophiles and CO2 to For the past fifteen years, reductive methylation using N-site-based nucleophiles and CO2 to give the corresponding methyl amines or formamide, which represents one of the most economical give the corresponding methyl amines or formamide, which represents one of the most economical give the corresponding methyl amines or formamide, which represents one of the most economical and environmentally friendly routes for C-N bond formation using CO as C building block has and environmentally friendly routes for C-N bond formation using CO2 as C1 building block has and environmentally friendly routes for C-N bond formation using CO2 as C1 building block has been investigated intensively. Recently, in this hot field, several groups such as Cantat (2015, been investigated intensively. Recently, in this hot field, several groups such as Cantat (2015, been investigated intensively. Recently, in this hot field, several groups such as Cantat (2015, reductive functionalization of CO with amines) [111,112], Yan (2015, transition metal-catalyzed reductive functionalization of CO2 with amines) [111,112], Yan (2015, transition metal-catalyzed reductive functionalization of CO2 with amines) [111,112], Yan (2015, transition metal-catalyzed methylation) [113], Beller (2017, catalytic methylation) [114], He (2018, transition-metal-free methylation) [113], Beller (2017, catalytic methylation) [114], He (2018, transition-metal-free methylation) [113], Beller (2017, catalytic methylation) [114], He (2018, transition-metal-free catalysis) [115], Kühn (2018, an update of CO catalytic conversion) [116], Fernández-Alvarez and catalysis) [115], Kühn (2018, an update of CO2 catalytic conversion) [116], Fernández-Alvarez and catalysis) [115], Kühn (2018, an update of CO2 catalytic conversion) [116], Fernández-Alvarez and Oro (2018, homogeneous catalytic reduction of CO with silicon-hydrides) [117], Motokura (2018, Oro (2018, homogeneous catalytic reduction of CO2 with silicon-hydrides) [117], Motokura (2018, Oro (2018, homogeneous catalytic reduction of CO2 with silicon-hydrides) [117], Motokura (2018, organocatalysis with silanes) [118], have reviewed the recent developments in CO hydrogenation organocatalysis with silanes) [118], have reviewed the recent developments in CO2 hydrogenation organocatalysis with silanes) [118], have reviewed the recent developments in CO2 hydrogenation based on amine substrates from different viewpoints. On the basis of the previous reviews and the based on amine substrates from different viewpoints. On the basis of the previous reviews and the based on amine substrates from different viewpoints. On the basis of the previous reviews and the integrityofthisarticle,here,theintroductionofthedevelopmentofCO conversionbasedonamines integrity of this article, here, the introduction of the development o2f CO2 conversion based on integrity of this article, here, the introduction of the development of CO2 conversion based on will be emphasized in a special view. The contents of this part include the regulatory strategies amines will be emphasized in a special view. The contents of this part include the regulatory amines will be emphasized in a special view. The contents of this part include the regulatory forfunctionalizationofCO forN-methylationandN-formylationofamineswithphenylsilaneand strategies for functionaliza2tion of CO2 for N-methylation and N-formylation of amines with strategies for functionalization of CO2 for N-methylation and N-formylation of amines with heterogeneous catalysis N-methylation of amines with CO and H . phenylsilane and heterogeneous catalysis N-methylation o2f amine2s with CO2 and H2. phenylsilane and heterogeneous catalysis N-methylation of amines with CO2 and H2. 3.1.RegulatoryFunctionalizationofCO withAminesandPhenylsilane:N-MethylationandN-Formylation 2 3.1. Regulatory Functionalization of CO2 with Amines and Phenylsilane: N-Methylation and N-Formylation 3.1. Regulatory Functionalization of CO2 with Amines and Phenylsilane: N-Methylation and N-Formylation of Amines of Amines of Amines In 2013, the methylation of amines was achieved using hydrosilanes as reductants through zinc In 2013, the methylation of amines was achieved using hydrosilanes as reductants through zinc In 2013, the methylation of amines was achieved using hydrosilanes as reductants through zinc complex catalysis by the Cantat group (Scheme 21) [119]. A mechanism going through a formamide complex catalysis by the Cantat group (Scheme 21) [119]. A mechanism going through a formamide complex catalysis by the Cantat group (Scheme 21) [119]. A mechanism going through a formamide intermediate was proposed. In recent years, many researchers undertook the study on selective intermediate was proposed. In recent years, many researchers undertook the study on selective intermediate was proposed. In recent years, many researchers undertook the study on selective catalysis of N-methylation and N-formylation of amines from amines, CO2, and hydrosilane. catalysis of N-methylation and N-formylation of amines from amines, CO2, and hydrosilane. catalysis of N-methylation and N-formylation of amines from amines, CO2, and hydrosilane. + NH R 0.1 MPa CO 0.1 MPa CO2 R Proposed mechanism Proposed mechanism H 5 mol% IPrZnCl2 H2 Me NN N 1 2equiv.PhSiH N 1 1 2 equiv. PhSiH3 1 R3R 2R 2R 22 RR Me O CO O CO2 2 Zn cat. R SiH Zn cat. R SiH Zn cat. R3SiH 1 Zn cat. R3SiH 3 1 1 R Me 2 THF, 100 oC, 20 h THF, 100 o C, 20 h 10-95% RN +RN 10-95% NH 2 122 12R RRNH 2 R R R NH 2 R SiOH R3SiOH R R (R Si) O 332 32 Scheme 21. Zinc complex-catalyzed methylation of amines using hydrosilanes.PDF Image | Catalytic Conversion of Carbon Dioxide through C-N Bond
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