Regio- and Stereo- Controlled Oxidations and Reductions, Volume 5

330 Pages·2007·6.24 MB·English

by  Stanley M. Roberts

Catalysts for Fine
Chemical Synthesis
Volume 5
Catalysts for Fine Chemical Synthesis, Vol. 5, Regio- and Stereo-Controlled Oxidations and Reductions
Edited by S. M. Roberts and J. Whittall © 2007 John Wiley & Sons, Ltd. ISBN: 978-0-470-09022-0
Catalysts for Fine Chemical Synthesis
Series Editors
Stanley M. Roberts
University ofManchester,UK
Ivan V. Kozhevnikov
University ofLiverpool,UK
Eric G. Derouane
UniversidadedoAlgarve,Faro,Portugal
Books in this Series
Volume 1: Hydrolysis, Oxidation and Reduction
EditedbyStanleyM.RobertsandGeraldinePoignant,University ofLiverpool,UK
ISBN: 978 0 471 98123 7
Volume 2: Catalysis by Polyoxometalates
EditedbyIvanK.Kozhevnikov, University ofLiverpool,UK
ISBN: 978 0 471 62381 6
Volume 3: Metal Catalysed Carbon-Carbon Bond-Forming Reactions
EditedbyStanleyM.RobertsandJianliangXiao,UniversityofLiverpool,UKandJohn
WhittallandTomE.Pickett, TheHeath,RuncornStylacats Ltd,UK
ISBN: 978 0 470 86199 8
Volume 4: Microporous and Mesoporous Solid Catalysts
EditedbyEric G.Derouane, UniversidadedoAlgarve,Faro,Portugal
ISBN: 978 0 471 49054 8
Volume 5: Regio- and Stereo-Controlled Oxidations and Reductions
EditedbyStanleyM.RobertsandJohnWhittall, University ofManchester,UK
ISBN: 978 0 470 09022 0
Catalysts for Fine
Chemical Synthesis
Volume 5
Regio- and Stereo-
Controlled Oxidations
and Reductions
Edited by
Stanley M. Roberts
University ofManchester,UK
John Whittall
University ofManchester,UK
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Regio-andstereo-controlledoxidationsandreductions/editedbyStanleyM.Roberts,JohnWhittall.
p.cm.– (Catalystsforfinechemicalsynthesis;v.5)
ISBN978-0-470-09022-0(cloth)
1. Oxidation.2. Reduction(Chemistry)3. Organiccompounds–Synthesis.
4. Catalysts. I.Roberts,StanleyM.II.Whittall,John.
QD281.O9R4362007
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Contents
SeriesPreface................................................. xvii
PrefacetoVolume5............................................ xix
Abbreviations ................................................ xxi
1 Industrial CatalystsforRegio-orStereo-SelectiveOxidationsandReductions
AReviewofKeyTechnologies andTargets ....................... 1
JohnWhittall
1.1 Introduction........................................... 2
1.2 Reduction ofCarbon-Carbon DoubleBonds .................... 3
1.2.1 Privilegedstructures:a-aminoacids anditaconicacids ........ 4
1.2.2 b-Aminoacids .................................... 5
1.2.3 a-Alkylsubstitutedacids ............................. 6
1.2.4 a-Alkoxysubstitutedacids............................ 8
1.2.5 Unsaturatednitriles................................. 9
1.2.6 Alkenesandallyl alcohols............................ 10
1.2.7 a,b-Unsaturated aldehydereduction...................... 10
1.3 Ketone andImineReduction ............................... 12
1.3.1 Catalytichydrogenationofketones andimines.............. 12
1.3.2 Asymmetrictransfer hydrogenation(ATH)catalysts .......... 15
1.3.3 Modifiedboranereagents............................. 20
1.3.4 Biocatalysts (alcoholdehydrogenasesandketoreductases)...... 21
1.4 Oxidation............................................. 23
1.4.1 Sharplesschiral epoxidation ofallylalcohols............... 23
1.4.2 Dioxiranecatalyzed epoxidation........................ 23
1.4.3 Aminesandiminiumsalts ............................ 25
1.4.4 Phasetransfer catalysts .............................. 25
1.4.5 TheJulia´–Colonnamethod (polyleucineoxidation)........... 26
1.4.6 Organocatalytic a-hydroxylation ofketones ................ 27
1.4.7 Baeyer–Villigeroxidation............................. 27
1.4.8 Chiralsulfoxides................................... 28
References............................................ 29
2 Asymmetric HydrogenationofAlkenes,Enones, Ene-Esters andEne-Acids 35
2.1 (S)-2,20-Bis{[di(4-methoxyphenyl)phosphinyl]oxy}-5,50,6,60,7,70,
8,80-octahydro-1,10-binaphthyl asaligandforrhodium-catalyzed
asymmetrichydrogenation................................. 36
IldikoGergely,CsabaHegedu¨sandJozsef Bakos
vi CONTENTS
2.1.1 Synthesisof(S)-5,50,6,60,7,70,8,80-Octahydro-1,10-bi-2-naphthol .. 37
2.1.2 Synthesisof(S)-2,20-Bis{[di(4-methoxyphenyl)phosphinyl]oxy}-
5,50,6,60,7,70,8,80-octahydro-1,10-binaphthyl. ................ 38
2.1.3 AsymmetrichydrogenationofDimethylitaconate............ 40
Conclusion............................................ 41
References............................................ 41
2.2 Synthesisandapplication ofphosphiniteoxazolineiridiumcomplexes
fortheasymmetric hydrogenationofalkenes.................... 42
FrederikMengesandAndreasPfaltz
2.2.1 Synthesisof(4S,5S)-2-(5-Methyl-2-phenyl-4,5-dihydro-oxazol-
4-yl)-1,3-diphenyl-propan-2-ol ......................... 42
2.2.2 Synthesisof(4S,5S)-O-[1-Benzyl-1-(5-methyl-2-phenyl-4,
5-dihydro-oxazol-4-yl)-2-phenyl-ethyl]-diphenylphosphinite..... 43
2.2.3 Synthesisof(4S,5S)-[(Z4-1,5-Cyclooctadiene)-{2-(2-phenyl-
5-methyl-4,5-dihydro-oxazol-4-yl)-1,3-diphenyl-2-
diphenylphosphinite-propane}iridium(I)]-tetrakis[3,
5-bis(trifluoromethyl)phenyl]borate ...................... 45
2.2.4 Asymmetrichydrogenationoftrans-a-Methylstilbene ......... 46
Conclusion............................................ 47
References............................................ 48
2.3 Synthesisandapplication ofheterocyclicphosphineoxazoline
(HetPHOX)iridiumcomplexesfortheasymmetrichydrogenation
ofalkenes ............................................ 48
FrederikMengesandPierGiorgioCozzi
2.3.1 Synthesisof(4S)-tert-Butyl-2-(thiophene-2-yl)-4,5-dihydrooxazole 49
2.3.2 Synthesisof(4S)-tert-Butyl-2-(3-diphenylphosphino-
thiophene-2-yl)-4,5-dihydrooxazole...................... 50
2.3.3 Synthesisof(4S)-[(Z4-1,5-Cyclooctadiene)-{4-tert-butyl-
2-(3-diphenylphosphino-thiophene-2-yl)-4,5-dihydrooxazole}
iridium(I)]-tetrakis[3,5-bis(trifluoromethyl)phenyl]borate ....... 52
2.3.4 Asymmetrichydrogenationoftrans-a-Methylstilbene ......... 53
Conclusion............................................ 54
References............................................ 54
2.4 (R)-2,20,6,60-Tetramethoxy-bis[di(3,5-dimethylphenyl)phosphino]-
3,30-bipyridine [(R)-Xyl-P-Phos] asaligandforrhodium-
catalyzedasymmetric hydrogenationofa-dehydroamino acids........ 55
JingWuandAlbertS.C.Chan
2.4.1 Synthesisof3-Bromo-2,6-dimethoxypyridine .............. 55
2.4.2 SynthesisofBis(3,5-dimethylphenyl)phosphinechloride ....... 56
2.4.3 Synthesisof3-Bromo-2,6-dimethoxy-4-di(3,5-dimethylphenyl)
phosphinopyridine.................................. 57
2.4.4 Synthesisof3-Bromo-2,6-dimethoxy-4-di(3,5-dimethylphenyl)
phosphinopyridine.................................. 59
2.4.5 2,20,6,60-Tetramethoxy-bis[di(3,5-dimethylphenyl)phosphinoyl]-
3,30-bipyridine .................................... 60
2.4.6 Opticalresolutionof((cid:2))-6 with((cid:3))or(þ)-2,3-O,O0-
Dibenzoyltartaric acidmonohydrate[(R)-6 or(S)-6)] ......... 61
2.4.7 (R)-2,20,6,60-Tetramethoxy-bis[di(3,5-dimethylphenyl)
phosphino]-3,30-bipyridine[(R)-Xyl-P-Phos, (R)-1]........... 62
2.4.8 Preparationofthestocksolutionof[Rh(R-Xyl-P-Phos)(COD)]BF 63
4
2.4.9 Atypicalprocedure fortheasymmetrichydrogenationof
methyl(Z)-2-Acetamidocinnamate. ...................... 64
References............................................ 65
CONTENTS vii
2.5 (R,R)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (QuinoXP*)
asaligandforrhodium-catalyzed asymmetrichydrogenationof
prochiralamino acidandaminederivatives....................... 65
TsuneoImamotoandAyaKoide
2.5.1 Synthesisof(R)-tert-Butyl(hydroxymethyl)methylphosphine–borane. 66
2.5.2 Synthesisof(R)-Benzoyloxy(tert-butyl)methylphosphine–borane ... 67
2.5.3 Synthesisof(S)-tert-Butylmethylphosphine–borane............. 69
2.5.4 (R,R)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (QuinoxP*)... 70
2.5.5 AsymmetrichydrogenationofMethyl(E)-3-acetylamino-2-
butenoatecatalyzed byRh(I)-(R,R)-2,3-Bis(tert-
butylmethylphosphino)quinoxaline ........................ 71
Conclusion.............................................. 72
References.............................................. 73
2.6 Rhodium-catalyzed asymmetrichydrogenationofindoles ............. 73
RyoichiKuwanoandMasayaSawamura
2.6.1 Synthesisof(R)-2-[(S)-1-(Dimethylamino)ethyl]-1-iodoferrocene... 73
2.6.2 Synthesisof(R)-2-[(S)-1-(Diphenylphosphinyl)ethyl]-
1-iodoferrocene...................................... 75
2.6.3 Synthesisof(R,R)-2,20-Bis[(S)-1-(diphenylphosphinyl)ethyl]-1,
100-biferrocene....................................... 78
2.6.4 Synthesisof(R,R)-2,200-Bis[(S)-1-(diphenylphosphino)ethyl]-1,
100-biferrocene [abbreviatedto(S,S)-(R,R)-PhTRAP]............ 80
2.6.5 Catalyticasymmetric hydrogenationofN-Acetyl-2-butylindole .... 82
2.6.6 Catalyticasymmetric hydrogenationof3-Methyl-N-
(p-toluenesulfonyl)indole ............................... 84
Conclusion.............................................. 85
References.............................................. 86
3 Asymmetric Reduction ofKetones................................ 87
3.1 (R,R)-Bis(diphenylphosphino)-1,3-diphenylpropaneasaversatile
ligandforenantioselectivehydrogenations........................ 89
NataliaDubrovinaandArmin Bo¨rner
3.1.1 Synthesisof(S,S)-1,3-Diphenylpropane-1,3-diol............... 89
3.1.2 Synthesisof(S,S)-Methanesulfonyloxy-1,
3-diphenylpropane-1,3-diol.............................. 91
3.1.3 Synthesisof(R,R)-Bis(diphenylphosphino)-1,3-diphenylpropane.... 91
Conclusion.............................................. 93
References.............................................. 93
3.2 Synthesisofbothenantiomersof1-Phenylethanolbyreductionof
acetophenonewithGeotrichumcandidum IFO5767................. 93
KaoruNakamura,MikioFujiiandYoshiteruIda
3.2.1 Cultivation ofG.candidumIFO5767...................... 94
3.2.2 Synthesisof(S)-1-Phenylethanol.......................... 95
3.2.3 Synthesisof(R)-1-Phenylethanol ......................... 95
Conclusion.............................................. 97
References.............................................. 97
3.3 Titanocene-catalyzed reductionofketonesinthepresence ofwater.
Aconvenientprocedure forthesynthesisofalcoholsvia
free-radical chemistry ...................................... 97
AntonioRosales,JuanM.CuervaandJ.EnriqueOltra
3.3.1 Titanocene-catalyzed reductionofAcetophenonein
thepresenceofwater.................................. 98
viii CONTENTS
3.3.2 Titanocene-catalyzed synthesisofMethyl4-deuterio-4-
phenyl-4-hydroxybutanoate.............................. 99
References.............................................. 100
3.4 Xyl-tetraPHEMP:ahighlyefficientbiarylligandinthe[diphosphine
RuCl diamine]-catalyzed hydrogenationofsimplearomaticketones ..... 101
2
PaulH.Moran,JulianP.Henschke,AntonioZanotti-GerosaandIanC.Lennon
3.4.1 SynthesisofTri(3,5-dimethylphenyl)phosphineoxide ........... 102
3.4.2 SynthesisofBis(3,5-dimethylphenyl)-(2-iodo-3,
5-dimethylphenyl)phosphineoxide ........................ 103
3.4.3 Synthesisofrac-4,40,6,60-Tetramethyl-2,20-bis[bis(3,
5-dimethylphenyl)phosphinoyl]-biphenyl .................... 105
3.4.4 Synthesisofrac-4,40,6,60-Tetramethyl-2,20-bis[bis(3,
5-dimethylphenyl)phosphino]-biphenyl[abbreviatedto
(rac)-Xyl-tetraPHEMP] ................................ 106
3.4.5 Synthesisof[(R)-N,N-Dimethyl(1-methyl)benzylaminato-
C2,N]-{rac-4,40,6,60-tetramethyl-2,20-bis[bis(3,5-dimethylphenyl)
phosphino]-biphenyl}-palladium(II) tetrafluoroborate and
separationofthediastereomers........................... 107
3.4.6 Synthesisof(S)-4,40,6,60-Tetramethyl-2,20-bis[bis(3,
5-dimethylphenyl)phosphino]-biphenyl:[abbreviatedto
(S)-Xyl-tetraPHEMP] and(R)-4,40,6,60-Tetramethyl-2,
20-bis[bis(3,5-dimethylphenyl)phosphino]-biphenyl[abbreviated
to(R)-Xyl-tetraPHEMP] ............................... 108
3.4.7 Synthesisof[(R)-Xyl-tetraPHEMP RuCl (R,R)-DPEN]
2
and[(S)-Xyl-tetraPHEMP RuCl (S,S)-DPEN] ................ 110
2
3.4.8 ReductionofAcetophenoneusing[(S)-Xyl-tetraPHEMP
RuCl (S,S)-DPEN]asaprecatalyst ....................... 111
2
Conclusion.............................................. 112
References.............................................. 112
3.5 N-Arenesulfonyl-andN-Alkylsulfamoyl-1,2-diphenylethylenediamine
ligandsforruthenium-catalyzed asymmetric transfer
hydrogenationofactivatedketones............................. 113
Michel(MassoudS.)StephanandBarbaraMohar
3.5.1 SynthesisofN-Arenesulfonyl-1,2-diphenylethylenediamines ...... 113
3.5.2 PreparationofRu(II)-N-arenesulfonyl-1,
2-diphenylethylenediamine complexes...................... 114
3.5.3 Asymmetrictransfer hydrogenationofEthyl
benzoylacetate ...................................... 115
Conclusion.............................................. 116
References.............................................. 116
3.6 Thesynthesisandapplication ofBrXuPHOS: anovelmonodentate
phosphorusligandfortheasymmetrichydrogenationofketones ........ 116
MartinWills, YingjianXu,GordenDochertyandGaryWoodward
3.6.1 Synthesisof(S)-BrXuPHOS ............................ 117
3.6.2 Synthesisof(S,S,SS)-BrXuPHOS-Ru-DPEN ................. 119
3.6.3 General procedureofasymmetrichydrogenation
ofacetophenone ..................................... 120
Conclusion.............................................. 121
Acknowledgement ........................................ 121
References.............................................. 121
3.7 InSituformationofligandand catalyst:application in
ruthenium-catalyzed enantioselectivereductionofketones............. 121
JennyWettergrenandHansAdolfsson
3.7.1 Synthesisof(S)-3-Fluoro-1-phenylethanol ................... 122
CONTENTS ix
Conclusion.............................................. 123
References.............................................. 124
3.8 SynphosandDifluorphosasligandsforruthenium-catalyzed
hydrogenationofalkenesandketones........................... 125
Se´verineJeulin,VirginieRatovelomanana-VidalandJean-PierreGenet
3.8.1 Synthesisof[RuCl((S)-SYNPHOS)(p-cymene)]Cl.............. 125
3.8.2 Synthesisof[RuCl((S)-DIFLUORPHOS)(p-cymene)]Cl.......... 126
3.8.3 Synthesisof[RuI((S)-DIFLUORPHOS)(p-cymene)]I............ 127
3.8.4 Synthesisof[NH R ][(RuCl(P*P)) (m-Cl) ]P*P¼
2 2 2 3
SYNPHOS orDIFLUORPHOSand R¼MeorEt.............. 127
3.8.5 Synthesisof[NH Me ][RuCl-(S)-DIFLUORPHOS] [m-Cl] ....... 128
2 2 2 3
3.8.6 Synthesisofinsitu generated[RuBr ((S)-SYNPHOS)]
2
and[RuBr ((S)-DIFLUORPHOS)]......................... 129
2
Conclusion.............................................. 131
References.............................................. 131
3.9 Anareneruthenium complexwithpolymerizable sidechainsforthe
synthesisofimmobilizedcatalysts ............................. 132
EstelleBurri, SilkeB.Wendicke,andKay Severin
3.9.1 Synthesisof2-Methyl-cyclohexa-2,5-dienecarboxylicacid
2-(2-methyl-acryloyloxy)-ethyl ester ....................... 133
3.9.2 Synthesisof[Z6-(2-Methyl-benzoic acid2-(2-methyl-
acryloyloxy)-ethylester)RuCl ] .......................... 134
22
Conclusion.............................................. 135
References.............................................. 135
3.10 Selectivereductionofcarbonylgroupinb,g-unsaturated
a-alpha-ketoesters bytransfer hydrogenationwithRu-(p-cymene)
(TsDPEN) .............................................. 135
MinjieGuo,DaoLi,YanhuiSunandZhaoguoZhang
3.10.1 Synthesis ofDi-m-chloro-bis[chloro(Z6-1-isopropyl-4-
methyl-benzene)ruthenium(II) ........................... 136
3.10.2 Synthesis of((cid:2))-Monotosylate-1,2-diphenyl-
1,2-ethylenediamine................................... 136
3.10.3 Synthesis ofRucomplexRu(p-cymene)(TsDPEN)............. 138
3.10.4 Ru-TsDPEN catalyzedtransfer hydrogenationreaction
ofb,g-unsaturated-a-ketoesters........................... 139
Conclusion.............................................. 140
References.............................................. 141
3.11 Preparation ofpolymer-supported Ru-TsDPENcatalystsandtheiruse
fortheenantioselectivesynthesisof(S)-fluoxetine.................. 141
LitingChai,YangzhouLiandQuanruiWang
3.11.1 Synthesis ofthesupported ligand9 ....................... 141
3.11.2 Synthesis ofligand17 ................................ 148
3.11.3General procedureforasymmetric
transfer hydrogenation................................. 150
3.11.4Preparation of(S)-Fluoxetinehydrochloride.................. 151
Conclusion.............................................. 154
References.............................................. 154
3.12 Polymer-supported chiralsulfonamide-catalyzed reductionof
b-keto nitriles:apractical synthesisof(R)-Fluoxetine................ 155
Guang-yinWangandGangZhao
3.12.1Synthesisof(R)-3-Amino-1-phenyl-propan-1-ol ............... 155
3.12.2Synthesisof(R)-ethyl 3-hydroxy-3-phenylpropylcarbamate ....... 156
3.12.3Synthesisof(R)-3-(Methylamino)-1-phenylpropan-1-ol.......... 157
3.12.4Synthesisof(R)-Fluoxetine ............................. 158
x CONTENTS
Conclusion............................................. 159
References............................................. 159
4 ImineReduction andReductiveAmination ........................ 161
4.1 Metal-free reductionofimines:enantioselectiveBrønsted
acid-catalyzed transfer hydrogenationusingchiral
BINOL-phosphates ascatalysts .............................. 162
MagnusRueping, ErliSugiono,CengizAzapandThomasTheissmann
4.1.1 Synthesisof(R)-2,20-Bis-methoxymethoxy-[1,10]binaphthalene
(MOM-BINOL) .................................... 162
4.1.2 Synthesisof(R)-3,30-Diiodo-2,20-bis(methoxymethoxy)-1,
10-binaphthalene .................................... 164
4.1.3 Synthesisof3,30-Bis-(3,50-bis-trifluoromethyl-phenyl)-2,
20-bismethoxymethoxy[1,10-binaphthalene] ................. 165
4.1.4 Synthesisof(R)-3,30-[3,5-Bis(trifluoromethyl)phenyl]-
1,10-binaphthylphosphate .............................. 166
4.1.5 General procedureforthetransfer hydrogenationofketimines.... 167
4.1.6 Synthesisof[1-(2,4-Dimethyl-phenyl)-ethyl]-
(4-methoxy-phenyl)-amine............................. 167
Conclusion............................................. 168
References............................................. 170
4.2 Metal-free Brønstedacid-catalyzed transferhydrogenation:
enantioselectivesynthesisoftetrahydroquinolines.................. 170
MagnusRueping, ThomasTheissmannandAndreyP.Antonchick
4.2.1 General procedureforthetransfer hydrogenationofquinolines ... 170
4.2.2 Synthesisof7-Chloro-4-phenyl-1,2,3,4-tetrahydroquinoline ...... 172
4.2.3 Synthesisof(S)-2-Phenyl-1,2,3,4-tetrahydroquinoline .......... 172
4.2.4 Synthesisof(R)-2-(2-(Benzo[1,3]dioxol-5-yl)ethyl)-1,2,3,
4-tetrahydro-quinoline................................ 173
Conclusion............................................. 174
References............................................. 174
4.3 Ahighlystereoselectivesynthesisof3a-Amino-23,
24-bisnor-5a-cholaneviareductiveamination. .................... 175
SharafNawazKhan, NamJuChoandHong-Seok Kim
4.3.1 SynthesisofTris[(2-ethylhexanoyl)oxy]borohydride ........... 177
4.3.2 Synthesisof3a-Acetamino-23,24-bisnor-5a-cholane .......... 177
4.3.3 Synthesisof3a-N-1-[N(3-[4-Aminobutyl])-1,
3-diaminopropane]-23,24-bisnor-5a-cholane ................ 179
Conclusion............................................. 181
Acknowledgements....................................... 181
References............................................. 181
5 OxidationofPrimaryandSecondaryAlcohols...................... 183
5.1 Copper(II)catalyzed oxidationofprimary alcohols
toaldehydeswithatmosphericoxygen ......................... 183
SuribabuJammiandTharmalinganPunniyamurthy
5.1.1 Synthesisofcopper(II) complex1........................ 184
5.1.2 Typicalprocedurefortheoxidationofprimaryalcohols
toaldehydes....................................... 185