Metathesis in natural product synthesis : strategies, substrates and catalysts PDF
Preview Metathesis in natural product synthesis : strategies, substrates and catalysts
This page intentionally left blank MetathesisinNaturalProductSynthesis Editedby JanineCossy,StelliosArseniyadis, andChristopheMeyer Related Titles Christmann,M.,Bra¨se,S.(eds.) Dalko,P.I.(ed.) AsymmetricSynthesis – The Enantioselective Essentials Organocatalysis ReactionsandExperimentalProcedures 395pageswith85figuresand3tables 2008 559pageswith364figuresand115tables Softcover 2007 ISBN:978-3-527-32093-6 Hardcover ISBN:978-3-527-31522-2 Hudlicky,T.,Reed,J.W. Cornils,B.,Herrmann,W.A.,Muhler,M., TheWayofSynthesis Wong,C.-H.(eds.) EvolutionofDesignandMethodsfor NaturalProducts Catalysisfrom A toZ AConciseEncyclopedia 1018pageswith285figuresand15tables 2007 approx.1560pagesin3volumeswith2778 Softcover figuresand104tables ISBN:978-3-527-31444-7 2007 Hardcover ISBN:978-3-527-31438-6 Sheldon,R.A.,Arends,I.,Hanefeld,U. Green ChemistryandCatalysis deVries,J.G.,Elsevier,C.J.(eds.) 448pageswith476figuresand21tables TheHandbookof 2007 HomogeneousHydrogenation Hardcover ISBN:978-3-527-30715-9 1641pagesin3volumeswith422figuresand 254tables 2007 Enders,D.,Jaeger,K.-E.(eds .) Hardcover AsymmetricSynthesiswith ISBN:978-3-527-31161-3 ChemicalandBiological Methods 470pageswith84figuresand57tables 2007 Hardcover ISBN:978-3-527-31473-7 Metathesis in Natural Product Synthesis Strategies, Substrates and Catalysts Edited by Janine Cossy, Stellios Arseniyadis, and Christophe Meyer With a Foreword by Robert H. Grubbs TheEditors AllbookspublishedbyWiley-VCHare carefullyproduced.Nevertheless,authors, Prof.JanineCossy editors,andpublisherdonotwarrantthe LaboratoriedeChimie informationcontainedinthesebooks, Organique,ESPCI includingthisbook,tobefreeoferrors. 10RueVauquelin Readersareadvisedtokeepinmindthat 75231ParisCedex05 statements,data,illustrations,procedural France detailsorotheritemsmayinadvertentlybe inaccurate. Dr.StelliosArseniyadis LaboratoiredeChimie LibraryofCongressCardNo.:appliedfor Organique,ESPCI 10RueVauquelin BritishLibraryCataloguing-in-Publication 75231ParisCedex05 Data France Acataloguerecordforthisbookisavailable fromtheBritishLibrary. Dr.ChristopheMeyer LaboratoiredeChimie Bibliographicinformationpublishedby Organique,ESPCI theDeutscheNationalbibliothek 10RueVauquelin TheDeutscheNationalbibliothekliststhis 75231ParisCedex05 publicationintheDeutscheNationalbibli- France ografie;detailedbibliographicdataareavail- ableontheInternetathttp://dnb.d-nb.de. Cover ©2010WILEY-VCHVerlagGmbH&Co. Thegryffonpaintingbeingpartofthefront KGaA,Weinheim coverpicturehasbeenkindlyprovidedby DominiqueEscortell Allrightsreserved(includingthoseof translationintootherlanguages).Nopart ofthisbookmaybereproducedinany form–byphotoprinting,microfilm,orany othermeans–nortransmittedortranslated intoamachinelanguagewithoutwritten permissionfromthepublishers.Registered names,trademarks,etc.usedinthisbook, evenwhennotspecificallymarkedassuch, arenottobeconsideredunprotectedbylaw. Cover AdamDesign,Weinheim Typesetting LaserwordsPrivateLimited, Chennai,India PrintingandBinding StraussGmbH, Mo¨rlenbach PrintedintheFederalRepublicofGermany Printedonacid-freepaper ISBN:978-3-527-32440-8 V Foreword In the last few decades, metathesis has been among the key reactions that have revolutionized the synthesis of complex molecules. Many organic chemists in academicandindustriallaboratories,inthefieldofnaturalproducts,haveusedthis reactionasaverypractical,versatile,andselectivesynthetictool.Olefinmetathesis hashelpedtoelevatetheartandscienceofchemicalsynthesistoitspresenthigh level. The examples in this book will demonstrate that organic chemists, with the metathesis reaction in hand, have a new way to consider the connections that are required for efficient access to natural products. This book assembles the most important and interesting examples in the synthesis of natural products using metathesis. Owing to the possibilities opened by olefin and acetylenic metathesis, a great variety of carbocyclic – nitrogen-, oxygen-, sulfur-containing heterocycles – natural products with small-, medium-, and macrocyclic size can beobtainedrapidly.Thesynthetictransformationsthatcouplemetathesisstepsin cascadereactionsareparticularlyelegant.Emphasishasbeenputonthemetathesis step showing the importance of the catalysts that are tolerant of a large variety of functional groups, very regio-, stereoselective, and even enantioselective. The power of the catalysts and of the metathesis reaction can be appreciated when alternativepathwaysareconsidered. Every reaction and catalyst can always be improved. In the area of metathesis, thedevelopmentofmoreactiveandrobustcatalysts,catalyststhatcancontrolthe EandZstereoselectivityoftheformedolefins,particularlythestereoselectivityof trisubstituted olefins, or catalysts that can control the enantioselectivity remains achallenge.Ashas beendemonstratedinthepast,improvementsofthecatalyts give rise to increasingly exciting applications in the field of complex molecules and particularly in the field of natural products synthesis. This book will be a goodsourceofinspirationforthoseplanningfuturedevelopmentsofmetathesis reactionsinthefieldofnaturalandnon-naturalproducts. RobertH.Grubbs MetathesisinNaturalProductSynthesis:Strategies,SubstratesandCatalysts.EditedbyJanineCossy, StelliosArseniyadis,andChristopheMeyer Copyright©2010WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim ISBN:978-3-527-32440-8 This page intentionally left blank VII Contents Foreword V Preface XV ListofCatalysts XIX ListofContributors XXI Abbreviations XXV 1 SynthesisofNaturalProductsContainingMedium-sizeCarbocyclesby Ring-closingAlkeneMetathesis 1 NicolasBlanchardandJacquesEustache 1.1 Introduction 1 1.2 FormationofFive-memberedCarbocyclesbyRCM 1 1.3 FormationofSix-memberedCarbocyclesbyRCM 11 1.4 FormationofSeven-memberedCarbocyclesbyRCM 22 1.5 FormationofEight-memberedCarbocyclesbyRCM 30 1.6 FormationofNine-memberedCarbocyclesbyRCM 33 1.7 Formationof10-memberedCarbocyclesbyRCM 34 1.8 Conclusion 39 References 40 2 NaturalProductsContainingMedium-sizedNitrogenHeterocycles SynthesizedbyRing-closingAlkeneMetathesis 45 Sebastiaan(Bas)A.M.W.vandenBroek,SilvieA.Meeuwissen, FlorisL.vanDelft,andFlorisP.J.T.Rutjes 2.1 Introduction 45 2.2 Five-memberedNitrogenHeterocycles 47 2.2.1 Dihydropyrroles 47 2.2.2 PyrrolidineAlkaloids 47 2.2.2.1 Pyrrolidines 47 2.2.2.2 Dipyrrolidines 49 2.2.2.3 Polyhydroxypyrrolidines 49 2.2.3 IndolizidineAlkaloids 52 2.2.3.1 PolycyclicIndolizidines 52 MetathesisinNaturalProductSynthesis:Strategies,SubstratesandCatalysts.EditedbyJanineCossy, StelliosArseniyadis,andChristopheMeyer Copyright©2010WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim ISBN:978-3-527-32440-8 VIII Contents 2.2.3.2 Polyhydroxyindolizidines 55 2.2.4 PyrrolizidineAlkaloids 59 2.3 Six-memberedNitrogenHeterocycles 61 2.3.1 PiperidineAlkaloids 61 2.3.1.1 Piperidines 61 2.3.1.2 PiperidineCarboxylicAcids 66 2.3.1.3 Piperidones 68 2.3.1.4 Polyhydroxypiperidines 69 2.3.2 IndolizidineAlkaloids 70 2.3.3 QuinolizidineAlkaloids 73 2.4 Seven-memberedNitrogenHeterocycles 78 2.5 Eight-memberedNitrogenHeterocycles 81 2.6 Conclusion 82 References 83 3 SynthesisofNaturalProductsContainingMedium-sizeOxygen HeterocyclesbyRing-closingAlkeneMetathesis 87 JonD.Rainier 3.1 Introduction 87 3.2 GeneralRCMApproachestoMediumRings 89 3.3 Laurencin 95 3.4 Eunicellins/Eleutherobin 102 3.5 Helianane 104 3.6 OctalactinA 105 3.7 MicrocarpalideandtheHerbarums 106 3.8 MarineLadderToxins 109 3.8.1 Ciguatoxin 109 3.8.2 Brevetoxin 117 3.8.3 Gambierol,GambiericAcid,Olefinic-ester Cyclizations 120 3.9 Conclusion 124 Acknowledgments 124 References 124 4 PhosphorusandSulfurHeterocyclesviaRing-closingMetathesis: ApplicationinNaturalProductSynthesis 129 ChristopherD.ThomasandPaulR.Hanson 4.1 Introduction 129 4.2 SynthesisandReactivityofSultonesDerivedfromRCM 129 4.3 TotalSynthesisoftheOriginallyProposedStructureof (±)-Mycothiazole 132 4.4 SynthesisandReactivityofPhosphatesfromRCM 134 4.5 ApplicationsofPhosphateTethersintheSynthesisof DolabelideC 140 4.6 Conclusion 144
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