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Molecules 2019, 24, 182 Molecules 2019, 24, x FOR PEER REVIEW Molecules 2019, 24, x FOR PEER REVIEW 29 of 41 29 of 42 29 of 42 Scheme 33. Proposed mechanism for reduction of aminal [131]. Scheme 33. Proposed mechanism for reduction of aminal [131]. 3.2.H3e.2te.rHoegtenroegoeunseoCuastCalaytsailyssMiseMtheythlaytlaiotinonofofAAmiineswithCO2 ananddHH2 Scheme 33. Proposed mechanism for red2 uction o2f aminal [131]. The use of hydrosilane could lead to the formation of large amount of siloxanes as by-products The use of hydrosilane could lead to the formation of large amount of siloxanes as by-products 3.2. Heterogeneous Catalysis Methylation of Amines with CO2 and H2 which is not beneficial to the development of sustainable chemistry. Therefore, in place of which is not beneficial to the development of sustainable chemistry. Therefore, in place of hydrosilane hydroTshielaunsee wofithydbreonsiiglanneHc2ouwlodulledadmtoakthe etfhoermhaytdiorongoefnlatrigoen amproucenstsofcsleilaonxearn. eIsnasadbyd-iptiroond, utchtes with benign H2 would make the hydrogenation process cleaner. In addition, the advantages awdhviacnhtaigsesnotf hbetneerfoicgieanl eotousthceatadlyevstelsoupcmh eanst eoasfilsyursetacionvaebrlye acnhdemreicsytrcyle. aTrheeroebfvoiroeu, si.nThpelarecfeoroef, of heterogeneous catalyst such as easily recovery and recycle are obvious. Therefore, herein, heyrderions,ihlaenterowgietnheobuesnicgantalHys2iswoonumldetmhyalkaetiotnheofhaymdirnoegsewnaithioCnOp2raoncdesHs 2cwleasnherig. hInligahdteddit.ion, the heterogeneous catalysis on methylation of amines with CO2 and H2 was highlighted. advaInta1g9e9s5,ofthheetBeariokgeerngeroouuspcaretaployrstesdutcheafsirestaseixlyamrepcloevoernythanedsyrnecthyecsleisaoref mobevthioyulasm. Tinhesreffrorme, In 1995, the Baiker group reported the first example on the synthesis of methylamines from ahmermeinon, hiae,tHer2oagnedneCoOus2 tchartaoluygshisCoun/mAle2tOh3yclatiaolnysotsf ainmainfeixsewd-ibthedCOm2icarnodreHac2twora(sShchigehmliegh34te)d[1. 34], but ammonia, H and CO through Cu/Al O catalysts in a fixed-bed microreactor (Scheme 34) [134], the eIfnfic1i29e9n5c,ythweaBsa2nikoetrhgigrohupenroeupgohrt.e2Sdutb3hseqfuiresnttelyxa,mthpelye otensttehdevsyarnitohuesistyopfesmoefthmyleatmali–naelsumfroinma butthcaametamelfyofisnctsiae(,CnHcuy2,aAwngda,PsCtOn,No2tih,hrCiogou,hgFhe)nCtouou/fAuglrh2tO.he3Srcuaibmtaspleyrqsotuvseinthtaleyf,cixatethadel-ybteitcdeasmctteicdvriotvireaesraiacotnoudrss(Setylcehpcetemisvieoti3fe4sm)[[1e13t3a54–l]–1,a3b7lu]t.mina catalyTthsheteseb(fCefsiucti,eaAnmcgiyn,ePwtpa,rsNodni,uoCcttoiho,ingFhera)ettenosoufwugerhrt.ehSeourbbtiamsienpqeurdoenvwteliytth,hCtehuce–ayMtatgelys–tAeicdl mavciatxireviodiutiosexstidyapensedsatsoe2fl8em0cte°iCtva,ilt–aianelsdum[o1vi3ne5ar–137]. ◦ 7 c a 9 t % a l s y e s l t e s c ( t C i v u i t , y A o g f , mP t e , t N h y i , l C a m o , i n F e e ) w t o a s f u o r b t h t a e i r n i e m d . p r o v e t h e c a t a l y t i c a c t i v i t i e s a n d s e l e c t i v i t i e s [ 1 3 5 – 1 3 7 ] . The best amine production rates were obtained with Cu–Mg–Al mixed oxides at 280 C, and over 79% The best amine production rates were obtained with Cu–Mg–Al mixed oxides at 280 °C, and over selectivity of methylamine was obtained. 79% selectivity of methylamine was obtained. Scheme 34. Heterogeneous metal-based catalysis methylation of ammonia. DuringSthcehepmaset3d4e.cHadeteryoegaernse,omuasnmyerteasl-ebaarscehdgcraotaulpysicsomnteitnhuyolautsiolyncoafrarmiedmonuitat.hestudyon Scheme 34. Heterogeneous metal-based catalysis methylation of ammonia. heterogeneous catalysis (Cu [138,139], Pd [140,141], Pt [142,143], Au [144,145], Re [146]) on DmuetrhinylgattiohneopfasmtidnescawditehyCeOa2rsa,nmd Han2,yanrdesaeasirgcnhifigcraonutprsocgorenstsinhuadoubeselyn mcaardrieetdotoalulyt(tThaeblsetu4)d.y on During the past decade years, many research groups continuously carried out the study on heterFohogetreneroxegaomeunspecloeau,tsaShlyciasatiasnld(yCsciuos -[w(1C3ou8rk,1e[31rs938]d,1eP3sdc9r][i,1b4ePd0d,1e[4f1f1e4]c0,t,iP1v4te1[]1h,4et2Pe,tr1o4[g31e4]n,2eA,1o4u3s[]1,c4aA4ta,u1ly4s[51t]4,s4yR,s1et4e[5m1]4,s6RC])euoA[n1lO4m6x]e[)t1h3oy8n]lation amnedthPydla/CtiounZroOf xam[1i4n0e]s fworiththCe Om2 eatnhdylHat2i,oanndofaasmiginiefsicawnithprCoOgr2esasnhdaHd 2beaesnsmouardcestoftoarllyth(eTambeleth4y)l. of amines with CO2 and H2, and a significant progress had been made totally (Table 4). For example, Shi gFrooruepx,amrepslpee,cSthiviealyn.dPcroi-mwaorrykearsndescerciobned eafrfeocmtiavteicheatnedrogaelnipehoautsiccaatmalyinsetssywstermescCounAvelOrtxe[d13t8o] and co-workers described effective heterogeneous catalyst systems CuAlOx [138] and Pd/CuZrOx [140] manedthPydla/mCuinZersOuxn[d1e4r0]thfeoridtehnetimcaeltrheyalcationso(1f7a0m°iCn,eHs 2w/CitOh2:C6O–72/a3nMdPHa)2. aIns tshoeurscaemsefoyreatrh,eShmimethizyul for the methylation of amines with CO2 and H2 as sources for the methyl group, respectively. egtroaulp. ,[1r4e2s]percetpivoertlyed. PariPmta-MryoOanx/dTiOse2cocnadtalyasrtominatitcheanmdethaylilpahtiaotnic oafmsienceosndwaeryre acmoinveesrtuedndetor Primary and second aromatic and aliphatic amines were converted to methylamines under the smoelvtheynlta-fmreienecsoundnditeiorntshe(0i.d5enMtiPcalCreOa2ctaionnds5(1M70P°aCH, H2)2./CBeOs2i:d6e–s7t/h3eMgPoao)d. Ipnetrhfoersmamaneceyeianr,thSheimwidzue identical reactions (170 ◦C, H2/CO2: 6–7/3 MPa). In the same year, Shimizu et al. [142] reported a sectoaple. o[f14se2c]ornedpaorryteadmianePs,t-tMheocOaxta/TlyiOst2wcastarelyusstedininthmeetmhyeltahtyiolantiofnN-omf estehcyolnadnairliyneawmiitnheCs Ou2nadnedr Pt-MoOx/TiO2 catalyst in the methylation of secondary amines under solvent-free conditions (0.5 MPa Hso2lvfoenr ta-ftrleeasctotnednitcioynclses(0w.5itMh Pnao CsiOgn2 ifaincadn5t lMosPsainHi2t)s. aBcetsividiteys. tNhoetagboloyd, tpherftortmalaTnOceNinduthriengwtihde CO and 5 MPa H ). Besides the good performance in the wide scope of secondary amines, the 2 sucocpcesosifvsec1o0nrdua2nrsyraemacihneds, t4h3e3chaitgahlyesrttwhans rTeOusNesdoinf tmhethoymlatoigoennoefoNus-mReuthcyatlalnyisltisn.eRwecitehnCtlyO,2tahnedy catalyaslstowsatusdrieudsTediOi2n-smupepthorytleadtiRonecoaftaNly-mste(Rthey/TliaOn2i)lipnreomwoithedCtOheNan-mdeHthyflaotrioantloefaasmttiennescybycleusiwngithno H2 for at least ten cycles with no significant loss in its activity.2Notably2, the total TON during the signifiHsuc2caacnetsdsloiCvsOes21in0[1ri4tu6sn].asRcrtei/vaTciithOye.2dNe4fof3itc3aiehbnilgytlh,ytehcraetthataolyntzaTeldOTNOthsNe ordefautchrteionhngoomthfoevgaserunioceucoesusasmRiviuenec1as0tianrlucylsnutsds.irnRegaecsehunebtdslyti4,tu3th3tehdyigher anlsiolinsteus,dtietdraThiyOd2r-souqpupinoorltiendesR,ealciapthaalytiscts(eRceo/nTdiOar2y) parmoimneosteidn 6th6e–9N9%-myeitehlydl.ation of amines by using than TONs of the homogeneous Ru catalysts. Recently, they also studied TiO2-supported Re catalyst H2 and CO2 [146]. Re/TiO2 efficiently catalyzed the reaction of various amines including substituted (Re/TiO2) promoted the N-methylation of amines by using H2 and CO2 [146]. Re/TiO2 efficiently anilines, tetrahydroquinolines, aliphatic secondary amines in 66–99% yield. catalyzed the reaction of various amines including substituted anilines, tetrahydroquinolines, aliphatic secondary amines in 66–99% yield.PDF Image | Catalytic Conversion of Carbon Dioxide through C-N Bond
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