TryptophantoindoleaminoacidwithLandDtypeType

Twoopticalisomers.Dtryptophanasanonreactiveprotein
Aminoacids,theirphysiologicalfunctionsandisstillintheresearchanddevelopmentstageof
preparation.Inthefoodandfeedindustryandagriculture,asnonnutritivesweetening
,Feedadditives,plantgrowthagent[1,2]andsoon.Inthepharmaceuticalindustry
In,Dtryptophanisusedtosynthesizeavarietyofpeptidedrugs,suchassomatostatin(Oxtreotide),
octreotideacetate(Sandostatinacetate),adrenocorticotropicpeptide25(Norleusacide),etc.,because
ofitssideChainpeptidebondsaredifficulttolactamenzyme,thesedrugshavebetter
Stabilityandresistancetodrugresistance[3].ButthehighpriceoftryptophanD
Gridlimititsapplication,therefore,Dtryptophansynthesisofa
ImportantDtryptophanmorepreparedforthefirstsynthesisofNacetylDLtryptophan
Acid,andthentogiveNacetylDtryptophanbytheselectivehydrolysisofthelast
Hydrolysistogivethedesiredproduct.
Forexample:(1)fromNacetamidomalonate
MalonateandacroleinsynthesisBenzalhydrazoneatlowtemperatures,inphenylhydrazone
Concentratedsulfuricacidorborontrifluoridecatalyzedcyclizationtogive3indolylA
Groupacetamidomalonate,theaqueoussodiumhydroxideselection
HydrolysistogiveNacetylDLtryptophan,thenchooseacylhydrolase
SelectivehydrolysisofNacetylDtryptophan,thenconcentratedhydroxide
SodiumhydrolyzedunderaqueousconditionsDtryptophan,thetotalyieldofonly
16.0%[4];(2)totheindoleasrawmaterial,anddimethylamine,formaldehyde
Mannichreactiongramine,thenwithNacetylglucosaminemalonate
Diethylsodiumhydroxideunderalkalineconditionscondensation,thenhydrolysisdecarboxylation
DLGiveNacetyltryptophan,aracemiccompoundthreo
Pnitrophenyl2amino1,3propanediolsplittogiveNacetyl
SaltgroupDtryptophanresolvingagentformedwithhydrochloricacidtoobtaintreatment
DNacetyltryptophan,thetargetproductcanbeobtainedfinallyhydrolysis,totalyield
31.5%[5,6].However,NacetyltryptophanhydrolysisD
Dtryptophanprocesspronetoracemizationsideeffects,iftheyaredirectly
SplitDLtryptophancaneffectivelyavoidtheoccurrenceofsidereactions,
SchemeDLtryptophanasfollows:(1)onitrotolueneoriginal
Material,andcondensationDMFDMAN,Ndimethyl2(2nitro
Phenyl)vinylamineafterwithdimethylamineandformaldehydesolutionatlowtemperatures
Thereactiontogive2(2nitrophenyl)propenal,withaNformylthen
Malonateringcondensedtogive1formyl5hydroxy4(2
Nitrophenyl)pyrrole2,2dicarboxylicacidester,atroomtemperature,thecompound
Catalytichydrogenationafterthecondensationof2formyl3(3indolyl)
2ethoxycarbonylpropionateinaqueoussodiumhydroxideandfinallywater
SolutionsdecarboxylationDLtryptophan,atotalyieldof64.5%[1]Thisoriginalroute

1Experimental
1.1Reagents
Gramine(reagentgrade,JintanMaoshengFineChemicalPlant);N
Acetamidomalonate(reagentgrade,NingboCreateBiologicalProject