Catalysis of Diels-Alder Reactions in Water

203 Pages·1998·1.066 MB·English

by  van der Woude F.

R IJKSUNIVERSITEIT G RONINGEN
C D A-
ATALYSIS OF IELS LDER
R W
EACTIONS IN ATER
Proefschrift
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negninor Gtietisrevinuskji Re dnaa
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899 1ilu j3gadjirv
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door
o tnteOrbjiS
geboren op 3 augustus 1971
negnino reGt
Promotor: Prof. Dr. J. B. F. N. Engberts
ISBN 90-367-0930-X
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Contents
C RETPAH 1 I NOITCUDORTN
1.1 I NOITCUDORTN ................................ ................................ ................................ ...................... 1
1.2 T EH D SLEI A- NOITCAE RREDL ................................ ................................ ................................ 2
1.2.1 History ................................ ................................ ................................ ........................... 3
2.2.1 citsinahceMstcepsa ................................ ................................ ................................ ........ 3
3.2.1 tnevloS stceffe no redlA-sleiDsnoitcaer ................................ ................................ .......... 8
4.2.1 dica-s iswiesLylatac fo redlA-sslneoiiDtcaer ................................ ................................ 11
1.3 W STCEF FCEIBOHPORD YDH NRAETA ................................ ................................ ................... 13
1.3.1 Hydrophobic hydration ................................ ................................ ................................ . 14
1.3.2 Hydrophobic interactions ................................ ................................ ............................. 17
1.4 S NROET A FWSOTCEF FLEAICEP D SLEI A- SNOITCAE RREDL ................................ ................... 18
1.4.1 ehT tceffe fo retaw no eht etar f oredlsAn-osilteciaDer ................................ ................ 18
2.4.1 ehT tceffe fo retaw no y teihvtit cr eseflndoeolsiAt-csaleeriD ................................ ....... 23
3.4.1 ehT tceffe fo sevitidda no eht etar dna ytivitceles fo redlA- sslneoiiDtcaer ni.retaw ...... 24
1.4.4 Synthetic applications ................................ ................................ ................................ ... 26
snoi tdaemtr ao5rf.es4 ln.dea1ecrtctaal-erRetaw ................................ ................................ ... 26
1.5 L DIC ASIWE -L RETA WN INOITANIDROO CESA BSIWE ................................ ........................... 27
1.5.1 tfoS-draH esaB-dicA )BASH(yroeht ................................ ................................ ............. 27
2.5.1 noitanidrooC ni retaw susrev cinagrostnevlos ................................ ............................. 28
1.6 M NOITAVITO , YDUT SSIH TF OENILTU ODN ASMIA ................................ ................................ 30
A STNEMEGDELWONKC ................................ ................................ ................................ .............. 31
N SECNEREF EDR NSAETO ................................ ................................ ................................ ........... 31
C RETPAH 2 L EWIS A- DIC C ATALYSIS
2.1 I NOITCUDORTN ................................ ................................ ................................ .................... 43
1.1.2 dica-siweL sisylatac fo cinagro snoitcaer ni suoeuqasnoitulos ................................ ..... 44
2.1.2 dica-siweL sisylatac fo redlA-sleiD snoitcaer ni suoeuqasnoitulos ............................... 47
2.2 R NOISSUCSI DDN ASTLUSE ................................ ................................ ................................ ... 48
2.2.1 Synthesis ................................ ................................ ................................ ...................... 50
2.2.2 tceffE fo eht tnevlos no eht etar fo eht desylatacnu.noitcaer ................................ ......... 51
2.2.3 Solvent and substituent effects on the Cu 2+ n odietscyaleartac- ................................ ...... 52
2.2.4 Variation of the catalyst ................................ ................................ ............................... 55
5y .to2ix.ve2i-tocdenlEes ................................ ................................ ................................ ...... 60
2.3 C SNOISULCNO ................................ ................................ ................................ ..................... 62
2.4 E NOITCE SLATNEMIREPX ................................ ................................ ................................ ...... 63
A XIDNEPP 2.1 ................................ ................................ ................................ ............................ 67
Contents
A TNEMEGDELWONKC ................................ ................................ ................................ ................ 68
N SECNEREF EDR NSAETO ................................ ................................ ................................ ........... 68
C RETPAH 3 L DNAGI E STCEFF - T OWARDS E NANTIOSELECTIVE L EWIS -
A DIC C ATALYSIS IN W ATER
3.1 I NOITCUDORTN ................................ ................................ ................................ .................... 75
1.1 .s3eidutS fo dna gsitlceffe nd oid cesasn-yosliiatwtceaaLce rniretaw ............................. 76
edvisicitasc-y esl2lia.ewt1sea.oLc3itnanE ................................ ................................ ........... 77
3.2 R NOISSUCSI DDN ASTLUSE ................................ ................................ ................................ ... 81
3.2.1 Effects of achiral ligands ................................ ................................ .............................. 81
3.2.2 Effects of L- a onima- dica sdnagil - gnippetS no eht liat foytivitcelesoitnane ................ 85
3.2.3 dnagiL - dnagil snoitcaretni ni yranret sexelpmoc - a erutaretilyevrus ......................... 87
4.2.3 stceffE fo sdnagil no eht oxe-odneytivitceles ................................ ................................ 90
3.2.5 Enantioselective catalysis ................................ ................................ ............................. 90
6.2.3 tnevloS tceffe noy teihvtitcelesoitnane ................................ ................................ .......... 94
7.2.3 snoitagitsevnI otni eht erutan fo eht enera - eneranoitcaretni ................................ ...... 96
3.3 C KOOLTU ODN ASNOISULCNO ................................ ................................ ............................ 100
3.4 E NOITCE SLATNEMIREPX ................................ ................................ ................................ ... 100
A STNEMEGDELWONKC ................................ ................................ ................................ ............ 102
N SECNEREF EDR NSAETO ................................ ................................ ................................ ......... 103
C RETPAH 4 T HE S FEOPOC L EWIS A- DIC C ATALYSIS OF D IELS A- LDER
R EACTIONS IN W ATER
4.1 I NOITCUDORTN ................................ ................................ ................................ .................. 107
1.1 .e4rutare tsimLialc fo dica -ssiiswyelLatac fo redl As-nsolieticDaer niretaw ................ 107
4.2 R NOISSUCSI DDN ASTLUSE ................................ ................................ ................................ . 110
1.2.4 erutaretiL selpmaxe fo dedia-yrailixuasisylatac ................................ ......................... 112
2.2.4 enizardyh)lydiryP-2( sa gnitanidroocyrailixua ................................ ........................... 113
4.2.3. A coordinating auxiliary via a Mannich reaction ................................ ....................... 114
4.3 C SNOISULCNO ................................ ................................ ................................ ................... 118
4.4 E NOITCE SLATNEMIREPX ................................ ................................ ................................ ... 118
N SECNEREF EDR NSAETO ................................ ................................ ................................ ................... 122
C RETPAH 5 M ICELLAR C ATALYSIS
5.1 I NOITCUDORTN ................................ ................................ ................................ .................. 125
1.1.5 ralleciM :setagergga erutcurts dnascimanyd ................................ ............................. 125
Contents
5.1.2 Solubilisation ................................ ................................ ................................ ............. 127
3.1.5 ralleciM sisylatac - citeniksledom ................................ ................................ .............. 129
4.1.5 ehT ecneulfni fo sellecim no redlA-sleiDsnoitcaer ................................ ...................... 131
5.2 R NOISSUCSI DDN ASTLUSE ................................ ................................ ................................ . 132
1.2 .s5tceffE fo sellecim ni eht ecnesba fo siweLsdica ................................ ......................... 132
2. 2s.t5ceffE f oselleci mni e hetcneser pfo siweLsdica ................................ ........................ 137
5.2.3 Average binding sites and their implications ................................ .............................. 144
5.3 C SNOISULCNO ................................ ................................ ................................ ................... 151
5.4 E NOITCE SLATNEMIREPX ................................ ................................ ................................ ... 142
A XIDNEPP 5.1 ................................ ................................ ................................ .......................... 154
A XIDNEPP 5.2 ................................ ................................ ................................ .......................... 154
A XIDNEPP 5.3 ................................ ................................ ................................ .......................... 155
A STNEMEGDELWONKC ................................ ................................ ................................ ............ 156
N SECNEREF EDR NSAETO ................................ ................................ ................................ ......... 156
C RETPAH 6 E EUGOLIP
6.1 I NOITCUDORTN ................................ ................................ ................................ .................. 161
6.2 G STNEMEVEIHC ADN ASLAO ................................ ................................ .............................. 161
6.3 L DIC ASIWE -L RETA WN ISNOITCARETN IESA BSIWE . I SISYLATA CRO FSNOITACILPM ......... 163
1.3.6 draH siweL sdica dnasesab ................................ ................................ ....................... 163
2.3.6 tfoS siweL sdica dnasesab ................................ ................................ .......................... 164
6.4 H STCEF FCEIBOHPORDY . I RETA WN IYTIVITCAE RCINAGR ORO FSNOITACILPM .................... 165
6.4.1 Hydrophobic hydration ................................ ................................ ............................... 166
6.4.2 Hydrophobic interactions ................................ ................................ ........................... 167
6.5 P HCRAES EERRUT U OFSTEVITNEC NDI NSATCEPSOR ................................ .......................... 169
N SECNEREF EDR NSAETO ................................ ................................ ................................ ......... 170
S YRAMMU ................................ ................................ ................................ .............................. 173
S GNITTAVNEMA ................................ ................................ ................................ ................... 179
Chapter 1
Introduction
sihT retpahc secudortni eht latnemirepxe krow debircsed ni eht gniwollof .sretpahc emoS
citsinahcem stcepsa fo eht redlA-sleiD noitcaer dna dica-siweL sisylatac foereht era.dessucsid
sihT retpahc stneserp a lacitirc yevrus fo eht erutaretil no tnevlos stceffe no redlA-sleiD,snoitcaer
htiw ralucitrap sisahpme no eht gniugirtni seitreporp fo retaw ni noitcennoc htiw rieht tceffeno
etar dna .ytivitceles ,ylralimiS eht stceffe fo retaw no siweL dica - siweL esab snoitcaretniera
discussed. Finally the aims of this thesis are outlined.
1.1 noitcudortnI
cinagrO yrtsimehc sah dah a dnuoforp ecneulfni no eht yaw eht namuh yteicos sah.depoleved
,sn keod ,nyinf d idtaosodr aroe dt r ofinu s aentrioenypv esrhobeareeatirhubcc tponccaianeargrO
a is ennnrnooo eii fdlttheel oacbsispruimaasnwp gesoracper a dleif .n eigcnnieri uceDsht tsalowt
seirutnec eht enilpicsid sah nees a suodnem e.rhttworg nI ruo yadyreve efil ew retnuocneynam
tnereffid stcudorp taht era sgnirpsffo fo eht tnassecni stroffe fo srehcraeser ni cinagro,yrtsimehc
.suoi v ebsrodanuop meosc esfhtotife n ee.hbsTenici dsoettmn ima op,rsfl esouptf amo osgrnfignar
y l sbn,gaornti e iitrvhrvaietberewinahowiptHe rtpi a nedru bo ttne mr nudoonraivn eni eht dneot
sevles rdunoa r.unoerdl iehhcT tes vonimoticteuflfoe sot snioh itmteullbloorpp si anoitcudefro
rieht .noitcudorp sA gnol sa siht si ton ,desilaer ti si fo tsomtu ecnatropmi ot ecudereht
.seitivit cra u fotocap mliatnemnorivne
A tynraecv iefcirnugoiss f onoitullo psi demrof yb eht c i,nsatgnreo vhlcoishw era desu nihcum
regr asleititnauq naht eht setulos yeht yrrac dna evah a ycnednet ot epacse otni ehttnemnorivne
hguorht noitaropave dna .egakae ldetanegola Hstnevlos era ylralucit rsaupoiroton htiw tcepserot
rieht cixot retcarahc dna roop .ytilibadargedoib A tol fo hcraeser si yltnerruc detoved oteht
tnempoleved fo eerf-tnevlos smetsys ro tnemecalper fo eht tnevlos yb a sselyllatnemnorivne
suodrazah .eno retaW si yllaedi detius rof siht esoprup gniwo ot sti cixot-non .retcarahcstI
suomrone ecnadnuba no siht tenalp sekam retaw a ylidaer elbisse c.ceavitanretla erehT eraosla
wei vf otnio pcimonoc en amor fsegatnavda 1 .
,yletanutro fmnoUrf a lacimehc tniop fo ,weiv ton lslnaoitamrofsn aerrta elbisaef ni nasuoeuqa
tn e.vmleotss yy s nseatsMnoepgm aonecer ehtdwhguo robt nticatn ohctiw retaw dna ynamsrehto
era tsomla elbulosni ni siht .tnevlos ,revoeroM retaw stcaretni ylgnorts htiw ynam,slacimehc
hy shcee.ltihr ttaihta ococ w w nta Nigmm o ermneoeifreeihrhtohhdtftct claoyelilhas ryebteirleht
.ts aep h ntsitsime hccinag rgono mtanevl orsalup oypr enave etb osn arhet a,wylgnisirprus
,yletanutroF ereht era osla a laitnatsbus rebmun fo lacimehc snoitamrofsnart taht era tonylno
sfcoitsiretcar aehucq iem nhotutriffe nyelbgno rytlslau tt,cumabui dseumo e h unteqailawbitapmoc
1