Biomimetic Organic Synthesis

976 Pages·2011·11.548 MB·English

by  Erwan Poupon, Bastien Nay

BiomimeticOrganicSynthesis
EditedbyErwanPouponandBastienNay
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Biomimetic Organic Synthesis
Volume 1
Alkaloids
Edited by Erwan Poupon and Bastien Nay
Biomimetic Organic Synthesis
Volume 2
Terpenoids, Polyketides, Polyphenols, Frontiers in Biomimetic
Chemistry
Edited by Erwan Poupon and Bastien Nay
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V
Foreword
The beauty and diversity of the biochemical pathways developed by Nature to
produce complex molecules is a good source of inspiration for chemists who
want to guided in their synthetic approach by biomimetic strategies. The first
biomimeticsyntheseswerereportedatthebeginningofthe20thcentury,withthe
famousexamplesofCollie’sandRobinson’srelatedtothesynthesisofphenolics
(orcinol)andalkaloids(tropinone).Sincethen,thenumberofreportedbiomimetic
syntheses, especially in the last twenty years, has increased, demonstrating the
power of these approaches in contemporary organic and bioorganic chemistry.
Biomimetic strategies allow the construction of complex natural products in a
minimumofstepswhichisinaccordancewiththe‘‘atomeconomy’’principleof
greenchemistryand,inaddition,simplereagentscanbeusedtoaccessthetargets.
Furthermore, the bioorganic consequences of such successful syntheses allow
the comprehension of the biosynthetic origin of natural compounds and these
processescanproducesufficientquantitiesofpureproductstoachievebiological
investigations.
The biomimetic synthesis field came to maturity thanks to interconnexions
betweenbiosyntheticstudiesandorganicsynthesis,especiallyinthetotalsynthesis
of complex molecules. Biomimetic syntheses could even be considered as the
latest stage of biosynthetic studies,confirming or invalidating the intimate steps
leading to natural product skeletons. For example, the Johnson’s polycyclization
of squalene precursors is one of the most impressive achievements in this field.
This is still organic synthesis as the reactions are taking place in the chemist’s
flaskunderchemicallycontrolledexperimentalconditions,whilebiosyntheticsteps
can involve enzymaticcatalysis, at least to acertain extent.However,concerning
complex biochemical transformations, the exact role of enzymes has not always
beenclear,andhasevenbeenquestionnedbysyntheticchemists.
Thetwobookvolumes‘‘BiomimeticOrganicSynthesis’’fillthegapintheorganic
chemistryliteratureoncomplexnaturalproducts.Thesebooksgather25chapters
from outstanding authors, not only dealing with the most important families
of natural products (alkaloids, terpenoids, polyketides, polyphenols...), but also
with biologically inspired reactions and concepts which are truly taking part in
biomimetic processes. By assembling these books, the editors E.Pouponand
B.Naysucceeded in gathering specialists in complex natural product chemistry
VI Foreword
for the benefit of the synthetic chemist community. With an educational effort
in discussions and schemes, and in comparing both the biosynthetic routes and
thebiomimeticachievements,thedemonstrationofthepowerofthebiomimetic
strategieswillbecomeobvioustothereadersinbothresearchandteachingareas.
These books will be a great source of inspiration for organic chemists and will
ensurethecontinueddevelopmentinthisexcitingfield.
ESPCI-ParisTechParis,France JanineCossy
VII
Contentsto Volume1
Preface XVII
ListofContributors XIX
BiomimeticOrganicSynthesis:anIntroduction XXIII
BastienNayandErwanPoupon
PartI BiomimeticTotalSynthesisofAlkaloids 1
1 BiomimeticSynthesisofOrnithine/ArginineandLysine-Derived
Alkaloids:SelectedExamples 3
ErwanPoupon,RimSalame,andLok-HangYan
1.1 Ornithine/ArginineandLysine:MetabolismOverview 3
1.1.1 Introduction:ThreeImportantBasicAminoAcids 3
1.1.2 FromPrimaryMetabolismtoAlkaloidBiosynthesis 5
1.1.2.1 l-OrnithineEntryintoSecondaryMetabolism 5
1.1.2.2 l-LysineEntryintoSecondaryMetabolism 5
1.1.3 CloselyRelatedAminoAcids 6
1.1.4 TheCaseofPolyamineAlkaloids 7
1.1.5 BiomimeticSynthesisofAlkaloids 8
1.2 BiomimeticallyRelatedChemistryofOrnithine-andLysine-Derived
ReactiveUnits 9
1.2.1 Ornithine-DerivedReactiveUnits 9
1.2.1.1 BiomimeticBehaviorof4-Aminobutyraldehyde 9
1.2.1.2 Dimerization 10
1.2.2 Lysine-DerivedReactiveUnits 11
1.2.2.1 OxidativeDegradationofFreel-Lysine 11
1.2.2.2 ClemensScho¨pf’sHeritage:50YearsofEndocyclicEnaminesand
TetrahydroanabasineChemistry 12
1.2.2.3 SpontaneousFormationofAlkaloidSkeletonsfrom
Glutaraldehyde 13
1.2.3 BiomimeticAccesstoPipecolicAcids 15
1.2.3.1 PipecolicAcids:BiosynthesisandImportance 15
1.2.3.2 BiomimeticAccesstoPipecolicAcids 16
VIII Contents
1.3 BiomimeticSynthesisofAlkaloidsDerivedfromOrnithineand
Arginine 18
1.3.1 BiomimeticAccesstothePyrrolizidineRing 18
1.3.2 BiomimeticSynthesesof ElaeocarpusAlkaloids 19
1.3.3 BiomimeticSynthesisofFissoldhimine 22
1.3.4 BiomimeticSynthesisofFicuseptine,Juliprosine,and
Juliprosopine 25
1.3.5 BiomimeticSynthesisofArginine-ContainingAlkaloids:
AnchinopeptolidesandEusynstyelamideA 26
1.3.5.1 NaturalProductsOverview 26
1.3.5.2 BiomimeticSynthesis 26
1.3.6 ACenturyofTropinoneChemistry 29
1.4 BiomimeticSynthesisofAlkaloidsDerivedfromLysine 30
1.4.1 AlkaloidsDerivedfromLysine:ToWhatExtent? 30
1.4.2 LupineAlkaloids 31
1.4.2.1 OverviewandBiosynthesisKeySteps 31
1.4.2.2 BiomimeticSynthesisofLupineAlkaloids 32
1.4.2.3 ABiomimeticConversionof N-MethylcytisineintoKuraramine 33
1.4.3 BiomimeticSynthesisof NitrariaandMyrioneuronAlkaloids 34
1.4.3.1 BiomimeticSynthesesofNitraramine 35
1.4.3.2 BiomimeticSynthesesofTangutorine 37
1.4.3.3 EndocyclicEnaminesOverview:BiomimeticObservations 39
1.4.4 BiomimeticSynthesisofStenusine,theSpreadingAgentof Stenus
comma 39
1.5 Pelletierine-BasedMetabolism 42
1.5.1 Pelletierine:ASmallAlkaloidwithaLongHistory 42
1.5.2 BiomimeticSynthesisofPelletierineandPseudopelletierine 43
1.5.2.1 Pelletierine(129) 43
1.5.2.2 Pseudopelletierine 44
1.5.3 LobeliaandSedumAlkaloids 44
1.5.4 LycopodiumAlkaloids 44
1.5.4.1 Overview,Classification,andBiosynthesis 44
1.5.4.2 BiomimeticRearrangementofSerratinineintoSerratezomineA 47
1.5.4.3 BiomimeticConversionofSerratinineintoLycoposerramineB 47
1.5.4.4 BiomimeticInterrelationswithintheLycoposerramineand
PhlegmariurineSeries 49
1.5.4.5 WhenChemicalPredispositionDoesNotFollowBiosynthetic
Hypotheses:Unnatural‘‘Lycopodium-Like’’Alkaloids 50
1.5.4.6 TotalSynthesisofCermizineCandSenepodineG 51
1.5.4.7 BiomimeticStepsintheTotalSynthesisofFastigiatine 52
1.5.4.8 BiomimeticStepsintheTotalSynthesisofComplanadineA 53
References 54