Asymmetric synthesis in organophosphorus chemistry: synthetic methods, catalysis, and applications

384 Pages·2017·17.886 MB·English

by  Oleg I. Kolodiazhnyi

AsymmetricSynthesisin
OrganophosphorusChemistry
Asymmetric Synthesis in
Organophosphorus Chemistry
SyntheticMethods,Catalysis,andApplications
OlegI.Kolodiazhnyi
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vii
Contents
Preface xi
Abbreviations xiii
1 FundamentalsoftheStereochemistryofOrganophosphorus
Compounds 1
1.1 HistoricalBackground 1
1.2 SomeCommonDefinitionsinStereochemistry 4
1.3 DeterminationofEnantiomerComposition 7
1.3.1 MethodofNuclearMagneticResonance 8
1.3.1.1 ChiralSolvatingAgents 8
1.3.1.2 ComplexesofMetals(ShiftReagents) 10
1.3.1.3 ChiralDerivatizingAgentsforNMR 11
1.3.2 ChromatographicMethodsofAnalysis 14
1.3.2.1 GasChromatography 15
1.3.2.2 LiquidChromatography 16
1.4 DeterminationoftheAbsoluteConfiguration 17
1.4.1 X-rayCrystalAnalysis 17
1.4.2 MethodofChemicalCorrelation 19
1.4.3 TheAssignmentofAbsoluteConfigurationbyNMR 19
1.5 AsymmetricInductionandStereochemistry 24
1.5.1 AsymmetricInduction 24
1.5.2 AsymmetricSynthesis 25
1.5.3 AsymmetricTransformation 25
1.5.4 AnEnantioselectiveReaction 25
1.5.5 EnantioselectiveSynthesis 25
1.6 Summary 26
References 26
2 AsymmetricSynthesisofP-ChirogenicPhosphorusCompounds 35
2.1 Introduction 35
2.2 Low-CoordinatedPhosphorusCompounds 36
2.3 TrivalentTricoordinatedPhosphorusCompounds 41
2.3.1 ConfigurationStabilityofP(III)-Compounds 41
2.3.2 AsymmetricNucleophilicSubstitutionatP(III) 43
2.3.2.1 SecondaryAlcoholsasChiralAuxiliaries 45
2.3.2.2 OpticallyActiveAminesasChiralAuxiliaries 54
viii Contents
2.3.2.3 EphedrineasInductorofChiralityatP(III) 58
2.3.3 AsymmetricOxidationofP(III)Compounds 67
2.3.4 AsymmetricElectrophilicSubstitutionatP(III) 68
2.3.4.1 AsymmetricMichaelis–ArbuzovReaction 70
2.4 PentavalentP(IV)-PhosphorusCompounds 71
2.4.1 Introduction 71
2.4.2 NucleophilicSubstitutionReactions 72
2.4.2.1 NucleophilicSubstitutionatP(IV)withChiralAlcohol 74
2.4.2.2 NucleophilicSubstitutionatP(IV)withChiralAmines 78
2.5 ChiralP(V)andP(VI)PhosphorusCompounds 80
2.6 Summary 86
References 87
3 PhosphorusCompoundswithChiralSide-ChainCenters 101
3.1 Introduction 101
3.2 AsymmetricInductioninSideChains 102
3.2.1 TransferofChiralityfromPhosphorustoOtherCenters 103
3.2.1.1 ChiralPhosphorus-StabilizedAnions 103
3.2.1.2 1,2-AsymmetricInduction 105
3.2.1.3 1,4-AsymmetricInduction 107
3.3 EnantioselectiveOlefination 113
3.4 StereoselectiveAdditionofPhosphorousNucleophilestoC=XBonds 117
3.4.1 Phospha-AldolReaction 119
3.4.2 Phospha-MannichReaction 130
3.4.3 Phospha-MichaelReaction 142
3.5 AsymmetricReduction 147
3.6 AsymmetricOxidation 152
3.7 C-Modification 156
3.8 AsymmetricCycloaddition 157
3.9 MultipleStereoselectivity 159
3.10 Summary 169
References 170
4 AsymmetricCatalysiswithMetalComplexes 187
4.1 Introduction 187
4.2 AsymmetricCatalyticHydrogenationandOtherReactionsof
Reduction 188
4.2.1 HydrogenationofC=CPhosphorusCompounds 188
4.2.2 HydrogenationofC=OPhosphorusCompounds 200
4.3 AsymmetricReductionandOxidation 203
4.3.1 ReductionofC=O,C=N,andC=Cbonds 204
4.3.2 AsymmetricOxidation 210
4.4 ElectrophilicAsymmetricCatalysis 211
4.4.1 CatalyticElectrophilicSubstitutionatthePhosphorusAtom 212
4.4.1.1 AlkylationandArylationofP(III)Compounds 213
4.4.2 CatalyticElectrophilicSubstitutioninaSideChain 217
4.4.2.1 Alkylation 217
4.4.2.2 Halogenation 219
Contents ix
4.4.2.3 Amination 221
4.5 NucleophilicAsymmetricCatalysis 223
4.5.1 AsymmetricAdditionofPhosphorusNucleophilestoMultipleBonds 223
4.5.1.1 Phospha-AldolReaction 224
4.5.1.2 Phospha-MannichReaction 229
4.5.1.3 Phospha-MichaelReaction 232
4.6 CycloadditionReactions 237
4.7 Summary 240
References 241
5 AsymmetricOrganocatalysis 253
5.1 Introduction 253
5.2 ModesforCatalyticActivationofSubstratesinAsymmetric
Organocatalysis 254
5.3 Phospha-AldolReaction 258
5.3.1 CatalysiswithCinchonaAlkaloids 258
5.3.2 CatalysiswithCinchona-Thiourea 259
5.3.3 CatalysisbyOtherOrganocatalysts 260
5.4 Phospha-MannichReactions 262
5.4.1 OrganocatalysisbyCinchonaAlkaloids 262
5.4.2 OrganocatalysisbyImines 263
5.4.3 OrganocatalysisbyIminiumsalts 265
5.4.4 OrganocatalysisbyChiralBrønstedacids 265
5.5 Phospha-MichaelReaction 269
5.5.1 OrganocatalysisbyCinchonaAlkaloids 269
5.5.2 OrganocatalysisbyThiourea 270
5.5.3 OrganocatalysisbyIminiumsalts 272
5.5.4 OrganocatalysisbyN-HeterocyclicCarbenes 274
5.5.5 OrganocatalysisUsingProlineDerivatives 274
5.6 OrganocatalyticAdditiontoKetophosphonates 282
5.6.1 Proline,AminoAcids,andTheirDerivatives 282
5.6.2 OrganocatalysisbyThiourea 288
5.7 Phospha-HenryReaction 288
5.8 OrganocatalyticModificationofP-ylids 290
5.9 AsymmetricCatalysiswithChiralDiamines 292
5.10 Miscellaneous 303
References 305
6 AsymmetricBiocatalysis 315
6.1 Introduction 315
6.2 EnzymaticSynthesisofOrganophosphorusCompounds 315
6.2.1 KineticResolutionofHydroxyphosphonates 316
6.2.2 Resolutionofα-HydroxyphosphonatesbyBiocatalytic
Transesterification 317
6.2.3 Resolutionofα-HydroxyphosphonatesbyBiocatalyticHydrolysis 319
6.2.4 DynamicKineticResolutionofα-Hydroxyphosphonates 323
6.2.5 Resolutionofβ-andω-Hydroxyphosphonates 323
6.2.6 DynamicKineticResolutionofβ-Hydroxyphosphonates 331
x Contents
6.2.7 ResolutionofAminophosphonates 332
6.3 BiosynthesisofCompoundswithC–PBond 335
6.4 ResolutionofP-ChiralPhosphorusCompounds 337
6.5 MicrobiologicalSynthesisofChiralOrganophosphorusCompounds 349
6.5.1 Yeast-CatalyzedSynthesis 349
6.5.2 SynthesisUsingUnicellularFungi 354
6.5.3 SynthesisUsingBacteria 356
6.6 Summary 358
References 358
Index 369
xi
Preface
Chiral phosphorus compounds play an important role in many areas of science,
includingbiologicallyactivepharmaceuticals,agrochemicals,andligandsfortransition
metal complexes. In the last few years, enormous success has been achieved in the
asymmetricsynthesisoforganophosphoruscompoundsandmanynewdevelopments,
finding considerable use in industry, have taken place,. Asymmetric synthesis and
asymmetriccatalysishavebeen,andremain,oneofthemostimportantresearchdirec-
tions in chemistry, attracting the interest of many scientists and chemical groups. As
aconsequence,theasymmetricsynthesisoforganophosphoruscompoundsisstudied
extensively in many scientific centers, including academic and industrial research
laboratories.Manymethodsforthepreparationofenantiomericallypureorganophos-
phorus compounds including classical resolution via diastereoisomers, chemical
kinetic resolution, enzymatic resolution, asymmetric metallocomplex catalysis, and
organocatalysis have been developed. Complexes with transition metals containing
PAMP, DIPAMP, DIOP, CHIRAPHOS ligands are widely used for the asymmetric
formation of C–H and C–C bonds. Over the last few years, great success has been
achievedintheasymmetricsynthesisoforganophosphoruscompounds,primarilywith
phosphineligandsforcatalyzedasymmetrichydrogenationreactions,andmanyarticles
devotedtothesynthesisofchiralorganophosphoruscompoundshavebeenpublished.
Inthelast10–15years,manyexcellentreviewsandmultivolumemonographsdedicated
tothestereochemistryoforganophosphoruscompoundshavebeenpublished.Several
journalsdedicatedtoasymmetricsynthesisandchirality,Tetrahedron:Asymmetryand
Chiralitybeingamongtheforemost,havealsogainedinpopularity.
Theimportanceofstereochemistryindrugactionanddifferencesinthephysiologic
action of enantiomeric antipodes is well-known and intensively studied now. The
requirements stipulated for new drugs by the Food and Drug Administration in the
UnitedStatesandbysimilarregulatingagenciesinothercountrieshasmadethismore
obvious.Someamino-andhydroxyphosphonicacids,aswellassyntheticphosphonic
acids,havebeenfoundtohaveeffectivemedicinalproperties;theyhavebeenapplied
in pharmacology and medicine. Detailed information about these functionalized
phosphonatesandphosphonicacidscanbefoundinthechaptersofthismonograph.
This book emphasize the importance of chiral organophosphorus compounds and
theirasymmetricsynthesis.Therehasbeennomonographdevotedtotheasymmetric
synthesisoforganophosphorusinthechemicalliteraturealthoughsuchastudywould
beofgreatinterest.Thisiswhatencouragedandinspiredustopreparethisbook.Our
bookisintendedtobeusedbychemistryexperimenters,professorsofuniversities,as
xii Preface
wellasresearchstudents,asasourceofbasicknowledgeandconvenientreference.The
literaturecoveredisupto2016.
Chapter 1 of this monograph is dedicated to the fundamentals of stereochemistry
of organophosphorus compounds, including general theoretical concepts, common
nomenclature, and analytical methods related to the stereochemistry of organophos-
phorus compounds. The other chapters of the book survey the various types of
asymmetricreactionsandchiralorganophosphoruscompounds.
Chapter2discussesmethodsforthesynthesisofcompoundswithchiralphosphorus
atoms,includingcompoundswithdicoordinatedphosphorusatom,three-coordinated
trivalentcompounds,compoundsoftetracoordinatedphosphorus,andalsocompounds
ofpentaandhexacoordinatedphosphorus,andsoon.
Chapter3describesthemethodsforasymmetricsynthesisofphosphoruscompounds
bearingchiralcentersinsidechains.Thesereactionsareparticularlyimportantforthe
productionofpharmaceuticalproductsandintermediates.
Chapter 4 presents asymmetric catalysis with complexes of transition metals,
that is, asymmetric catalytic hydrogenation and stoichiometric reduction of various
unsaturatedcompounds.Asymmetrichydrogenationisthesimplestwaytocreatenew
chiralcentersandthetechnologyisaflagshipforchiralsynthesis.Becauseasymmetric
synthesis is a highly application-oriented science, examples of industrial applications
oftherelevanttechnologiesareappropriatelyillustratedthroughoutthetext.
Chapter5isdevotedtoorganocatalysis,whichisespeciallyintensivelyinvestigated.
The most important principles of organocatalysis and examples of preparative and
practical applications are discussed. In particular, the use of alkaloids of quinine and
its derivatives, sparteine, proline, and amino acid and their derivatives as catalysts is
described.
Chapter6considerstheuseofenzymesandothersbiologicalmethodsinasymmetric
synthesis. Methods of kinetic resolution of racemic organophosphorus compounds,
biocatalytictransesterification,dynamickineticresolutionofα-hydroxyphosphonates,
enzymaticresolutionofaminophosphonates,andthebiosynthesisofcompoundswith
C–Pbondsarediscussed.Microbiologicalsynthesisofchiralphosphoruscompounds
withyeast,bacteria,fungiareconsidered.
Thebookdiscussesmethodsfortheasymmetricsynthesisofchiralorganophospho-
rus compounds with many applications in stereoselective synthesis and asymmetric
catalysis with reference to updated literature findings as well as the author’s original
researchesperformedoverthelast15–20years.
KolodiazhnyiO.