Progress in the Chemistry of Organic Natural Products PDF
Preview Progress in the Chemistry of Organic Natural Products
W0 88 Fortschritte der Chemie organischer Naturstoffe Progress in the Chemistry of Organic Natural Products Founded by L. Zechmeister Edited by W. Herz, H. Falk, and G. W. Kirby Authors: J. F. Grove, E. Reimann, S. Roy SpringerWienNewYork Prof.W.Herz,DepartmentofChemistry, TheFloridaStateUniversity,Tallahassee,Florida,U.S.A. Prof.H.Falk,Institutfu¨rChemie, Johannes-Kepler-Universita¨t,Linz,Austria Prof.G.W.Kirby,ChemistryDepartment, TheUniversityofGlasgow,Glasgow,Scotland Thisworkissubjecttocopyright. Allrightsarereserved,whetherthewholeorpartofthematerialisconcerned,specifically those of translation, reprinting, re-use of illustrations, broadcasting, reproduction by photocopyingmachinesorsimilarmeans,andstorageindatabanks. #2007Springer-Verlag=Wien PrintedinAustria SpringerWienNewYorkispartof SpringerScienceþBusinessMedia springer.com ProductLiability:Thepublishercangivenoguaranteefortheinformationcontainedinthis book.Thisalsoreferstothatondrugdosageandapplicationthereof.Ineachindividualcase therespectiveusermustchecktheaccuracyoftheinformationgivenbyconsultingother pharmaceuticalliterature.Theuseofregisterednames,trademarks,etc.inthispublication does not imply, even in the absence of a specific statement, that such names are exempt fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. LibraryofCongressCatalogCardNumberAC39-1015 Typesetting:ThomsonPress(India)Ltd.,Chennai Printingandbinding:DruckereiTheissGmbH,A-9431St.Stefan Printedonacid-freeandchlorine-freebleachedpaper SPIN:10975961 With12Figuresand1colouredPlate ISSN0071-7886 ISBN-10 3-211-20688-4 SpringerWienNewYork ISBN-13 978-3-211-20688-1 SpringerWienNewYork Contents ListofContributors............................................. IX SynthesisPathwaystoErythrinaAlkaloids andErythrinaTypeCompounds E.Reimann ................................................. 1 1. Introduction............................................... 2 2. StructuralClassificationofErythrinaAlkaloids ...................... 4 3. NewErythrinaAlkaloids...................................... 18 4. BiosynthesisofErythrinaAlkaloids.............................. 18 4.1. ErythrinaneAlkaloids..................................... 18 4.2. HomoerythrinaneAlkaloids................................. 20 5. SynthesesofErythrinaAlkaloidsandErythrinaTypeCompounds......... 21 5.1. MethodicalClassification .................................. 22 5.2. Erythrinanes ........................................... 23 5.2.1. FinalFormationofOneRing........................... 23 5.2.1.1. RingC(RouteC)............................. 23 5.2.1.1.1. CyclizationofN-Phenethylhydroindole Derivatives(RouteC(a)) ................ 23 5.2.1.1.2. CyclizationofAngularyArylatedHydroindole Derivatives(RouteC(b)) ................ 29 5.2.1.2. FormationofRingB(RouteB) ................... 32 5.2.1.2.1. CyclizationofN-substituted C5-SpiroisoquinolineDerivatives (RouteB(a)) ........................ 32 5.2.1.2.2. CyclizationofC6-Substituted C5-SpiroisoquinolineDerivatives (RouteB(b)) ........................ 35 5.2.1.3. FormationofRingA(RouteA)................... 35 5.2.1.3.1. CycloadditiontoPyrroloisoquinolines (RouteA(a)) ........................ 35 5.2.1.3.2. IntramolecularAldolCondensation ofAngularlySubstitutedPyrroloisoquinoline (RouteA(b)) ........................ 37 5.2.2. SimultaneousFormationofMoreThanOneRing............. 38 5.2.2.1. SimultaneousFormationofRingsB andC(RouteB/C)............................ 39 VI Contents 5.2.2.1.1. CyclizationofSecondaryDiphenethyl- or(Cycloalkyl)ethyl-phenethylamineDerivatives (RouteB/C(a)) ......................... 39 5.2.2.1.2. CyclizationofTertiaryCyclohexyl-ethyl- phenethyl-amideDerivatives (RouteB/C(b)) ........................ 42 5.2.2.2. CyclizationofN-Substituted1-Acyldihydroisoquinolinium Derivatives(RouteA/B) ........................ 44 5.2.2.3. CyclizationofaHighlyFunctionalized Homoveratrylimide(RouteA/B/C)................. 45 5.3. Homoerythrinanes ....................................... 45 5.3.1. BiomimeticRoutes.................................. 47 5.3.2. FinalCRingFormationStartingfromN-Substituted Phenylhydroindoles.................................. 49 5.3.3. ARingFormationby[2þ2]Photocycloaddition toPyrrolobenzazepines ............................... 50 5.3.4. SimultaneousBRingFormation/CRingExpansion StartingfromSpiro-2-tetralones......................... 52 6. Pharmacology ............................................. 53 7. ConcludingRemarks......................................... 55 References.................................................. 56 TheTrichothecenesandTheirBiosynthesis J.F.Grove(y) ............................................... 63 1. Introduction............................................... 63 2. TheTrichothecenes.......................................... 64 2.1. MacrocyclicandNon-MacrocyclicCompounds................... 64 2.2. TrichotheceneRelatives ................................... 90 2.3. Sources............................................... 96 2.4. OxygenationPattern...................................... 97 3. Biosynthesis............................................... 98 3.1. SimpleTrichothecenes.................................... 98 3.1.1. MevalonicAcidtoTrichodiene ......................... 98 3.1.2. Trichodieneto12,13-EpoxytrichotheceneandIsotrichodermol.... 101 3.1.3. FurtherOxygenationandEsterificationoftheTrichothecene Nucleus:BiosynthesisofSpecificMetabolites ............... 104 3.1.3.1. Trichothecolone .............................. 104 3.1.3.2. VomitoxinandDerivatives....................... 104 3.1.3.3. T-2Toxin................................... 107 3.1.3.4. NivalenolandDerivatives ....................... 108 3.1.4. TrichotheceneBiosyntheticGeneClusters.................. 108 3.2. TrichoverroidsandMacrocyclicTrichothecenes................... 109 3.3. TrichotheceneRelatives ................................... 112 References.................................................. 113 Contents VII Melanin,Melanogenesis,andVitiligo S.Roy..................................................... 131 1. Melanin.................................................. 132 1.1. Introduction ........................................... 132 2. ChemistryofMelanin........................................ 134 2.1. IsolationandAnalysis .................................... 134 2.2. Solubilization .......................................... 135 2.3. ProteinContent......................................... 135 2.4. CarboxylicandPhenolicFunction............................ 136 2.5. ChemicalDegradation .................................... 136 2.5.1. ReductiveMethods.................................. 136 2.5.2. OxidativeMethods.................................. 137 2.5.3. PyrolyticMethods .................................. 137 2.6. SpectroscopicStudies..................................... 138 2.6.1. UVandIRSpectroscopy.............................. 138 2.6.2. NMRSpectroscopy.................................. 138 2.6.3. X-RayDefractionStudy .............................. 138 2.6.4. ESRStudy........................................ 139 2.7. StructureofMelanin ..................................... 139 2.7.1. MelaninasHomopolymer............................. 139 2.7.2. MelaninasPoikilopolymer ............................ 140 2.7.3. MelaninasBipolymer................................ 141 2.7.4. BiophysicalModelofMelaninStructure................... 141 2.7.5. StructureofPhaeomelanin............................. 143 2.8. SynthesisofMelanin..................................... 143 2.8.1. ElectrochemicalSynthesis............................. 143 2.8.2. PhotochemicalSynthesis.............................. 145 3. CharacteristicBiophysicochemicalPropertiesofMelanin ............... 145 3.1. InteractionofMelaninwithLight ............................ 146 3.1.1. MelanininUVandVisibleLight........................ 146 3.1.2. MelanininthePhotoprotectionofSkin.................... 146 3.1.3. MelaninasLightScreeninEyes ........................ 147 3.2. MelaninandItsRedoxFunction ............................. 148 3.3. BindingComplexationandMedicinalAspectsofMelanin ........... 149 3.4. UseofMelaninforDefence ................................ 150 4. Melanogenesis............................................. 150 4.1. Melanogenesisinvivo .................................... 150 4.1.1. Melanocytes....................................... 151 4.1.2. TheCharacteristicsoftheEnzyme....................... 152 4.1.3. RegulationofMelanogenesis........................... 153 4.1.3.1. PhysiologicalFactors........................... 154 4.1.3.2. OrganicSulfurCompounds ...................... 154 4.1.3.3. MetalIonsandOtherChemicals................... 154 4.1.3.4. Vitamins ................................... 154 4.1.3.5. Hormones .................................. 155 4.1.3.6. NeuralInfluence.............................. 157 4.1.3.7. MalpighianCells ............................. 157 4.1.3.8. UVLight................................... 157 VIII Contents 4.2. Melanogenesisinvitro.................................... 157 4.2.1. EnzymaticMelaninSynthesis........................... 157 4.2.1.1. RearrangementofDopachrome.................... 158 4.2.1.2. PolymerizationofDHI ......................... 159 4.2.2. Non-EnzymaticMelaninSynthesis:ModelReaction........... 161 4.2.2.1. UdenfriendSystem:AModelforMixedFunction Oxidase.................................... 161 4.2.2.2. MelaninFormationUnderUdenfriendConditions....... 162 5. Vitiligo.................................................. 164 5.1. Introduction ........................................... 164 5.2. Melanocytotoxicity:Antimelanocyte-AntibodiesFormation........... 164 5.2.1. TheImmuneHypothesis.............................. 165 5.2.2. TheNeuralHypothesis ............................... 165 5.2.3. TheSelf-DestructionHypothesis ........................ 165 5.2.4. TheCompositeHypothesis ............................ 165 5.3. ChemotherapyofVitiligo.................................. 166 5.3.1. Psoralens......................................... 166 5.3.2. PsoralenActionandUVLight.......................... 166 5.3.3. PsoralenActiononMelanogenesis....................... 167 5.4. AbnormalBiochemicalParametersinVitiligo.................... 168 5.5. StatusofTryptophanintheMelanogenicSystem ................. 169 5.6. ACompositeHypothesisonVitiligo .......................... 171 References.................................................. 171 AuthorIndex ............................................... 187 SubjectIndex ............................................... 201 List of Contributors Grove, Dr. J. F., 3 Homestead Court, Welwyn Garden City, Herts AL7 4LY, England (deceased) Reimann, Prof. Dr. E., Department of Pharmacy, Ludwig-Maximilians-Universita¨t, Butenandtstrasse5–13,81377Mu¨nchen,Germany, e-mail:[email protected] Roy, Dr. S., Institute of Natural Products, 8 J. N. Roy Lane, Kolkata 700006, India, e-mail:[email protected] Synthesis Pathways to Erythrina Alkaloids and Erythrina Type Compounds Eberhard Reimann DepartmentofPharmacy, Ludwig-Maximilians-Universita¨tMu¨nchen,Germany Contents 1. Introduction............................................... 2 2. StructuralClassificationofErythrinaAlkaloids ...................... 4 3. NewErythrinaAlkaloids...................................... 18 4. BiosynthesisofErythrinaAlkaloids .............................. 18 4.1. ErythrinaneAlkaloids..................................... 18 4.2. HomoerythrinaneAlkaloids................................. 20 5. SynthesesofErythrinaAlkaloidsandErythrinaTypeCompounds ......... 21 5.1. MethodicalClassification .................................. 22 5.2. Erythrinanes ........................................... 23 5.2.1. FinalFormationofOneRing........................... 23 5.2.1.1. RingC(RouteC)............................. 23 5.2.1.1.1. CyclizationofN-Phenethylhydroindole Derivatives(RouteC(a)) ................. 23 5.2.1.1.2. CyclizationofAngularyArylatedHydroindole Derivatives(RouteC(b)) ................ 29 5.2.1.2. FormationofRingB(RouteB) ................... 32 5.2.1.2.1. CyclizationofN-substituted C5-SpiroisoquinolineDerivatives (RouteB(a)) ......................... 32 5.2.1.2.2. CyclizationofC6-Substituted C5-SpiroisoquinolineDerivatives (RouteB(b)) ......................... 35 5.2.1.3. FormationofRingA(RouteA) ................... 35 5.2.1.3.1. CycloadditiontoPyrroloisoquinolines (RouteA(a)) ......................... 35 5.2.1.3.2. IntramolecularAldolCondensation ofAngularlySubstitutedPyrroloisoquinoline (RouteA(b)) ......................... 37 5.2.2. SimultaneousFormationofMoreThanOneRing............. 38 5.2.2.1. SimultaneousFormationofRingsB andC(RouteB/C) ............................ 39
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