Transition metal mediated, enantioselective synthesis of novel carbocyclic nucleoside analogs with strong apoptosis-inducing properties:
Gespeichert in:
| 1. Verfasser: | |
|---|---|
| Format: | Abschlussarbeit Buch |
| Sprache: | English |
| Veröffentlicht: |
2002
|
| Schlagworte: | |
| Online-Zugang: | Inhaltsverzeichnis |
| Beschreibung: | XVIII, 227 S. Ill., graph. Darst. 30 cm |
Internformat
MARC
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| 100 | 1 | |a Velčický, Juraj |e Verfasser |4 aut | |
| 245 | 1 | 0 | |a Transition metal mediated, enantioselective synthesis of novel carbocyclic nucleoside analogs with strong apoptosis-inducing properties |c vorgelegt von Juraj Velčický |
| 264 | 1 | |c 2002 | |
| 300 | |a XVIII, 227 S. |b Ill., graph. Darst. |c 30 cm | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 502 | |a Köln, Univ., Diss., 2003 | ||
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Datensatz im Suchindex
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M
CONTENTS
PAGE
1 INTRODUCTION I
1.1 CANCER 1
1.2
APOPTOSIS - A PROGRAMMED CELL DEATH (PCD)
6
1.3
CARBOCYCLIC NUCLEOSIDE ANALOGS (CNAS)
14
1.3.1
INTRODUCTION 14
1.3.1.1
METHODS FOR THE COUPLING OF NUCLEOBASES WITH CARBOCYCLIC
PSEUDO SUGARS
17
1.3.2.1 CONVERGENT ATTACHMENT OF NUCLEOBASES BY SUBSTITUTION REACTIONS
17
1.3.1.1.1
PALLADIUM-CATALYZED ALLYLIC SUBSTITUTION 18
1.3.1.1.2
MITSUNOBU COUPLING 20
1.3.2.2 LINEAR CONSTRUCTION OF NUCLEOBASES FROM AN AMINE SUBSTITUENT
ON THE CARBOCYCLIC CORE 20
1.3.3
SYNTHETIC METHODS FOR THE CONSTRUCTION OF CYCLOPENTYL NA 21
1.3.3.1 MODIFICATION OF EASILY AVAILABLE FUNCTIONALIZED CYCLOPENTANE
- DERIVATIVES 21
1.3.3.2 CONSTRUCTION OF THE CYCLOPENTYL SKELETON 23
1.4
IRON-CONTAINING NA AS POTENTIAL ANTI-CANCER DRUGS
28
1.4.1
UTILIZATION OF ORGANOMETALLIC COMPOUNDS IN MEDICAL TREATMENT 28
1.4.2
SYNTHESIS OF IRON-CONTDINING NA WITH A FURANOSE-TYPE BACKBONE 29
2 A STRATEGY FOR THE SYNTHESIS OF NOVEL CARBOCYCLIC
NUCLEOSIDE ANALOGS (CNA)
32
2.1
INTRODUCTION
32
2.2
SYNTHETIC STRATEGY
32
BIBLIOGRAFISCHE INFORMATIONEN
HTTP://D-NB.INFO/968408672
IV
3 RESULTS AND DISCUSSION
37
3.1
SYNTHESIS OF PRECURSORS FOR THE PAUSON-KHAND
REACTION (PKR)
37
3.2
THE PAUSON-KHAND REACTION (PKR)
39
3.3
SYNTHESIS OF PRECURSORS FOR THE INTRODUCTION OF
NUCLEOBASES
44
3.4
KINETIC RESOLUTION
47
3.4.1
INTRODUCTION
47
3.4.2
KINETIC RESOLUTION (KR) BY MEANS OF ASYMMETRIC REDUCTION
48
3.4.3
DETERMINATION OF THE ABSOLUTE CONFIGURATION
55
3.4.3.1 CD-SPECTROSCOPY 55
3.4.3.2 MOSHER'S ESTER ANALYSIS 59
3.4.4
ENZYMATIC KINETIC RESOLUTION
62
3.5
PREPARATION OF UNIVERSAL PRECURSORS FOR TWO
TYPES OF CNAS
62
3.5.1
PD-CATALYZED NUCLEOBASE INTRODUCTION
62
3.5.2
HYDROLYSIS OF BICYCLIC ACETATES
66
3.6
SYNTHESIS OF IRON-FREE CNAS
68
3.7
SYNTHESIS OF IRON-CONTAINING CNAS
73
3.8
RESULTS OF BIOLOGICAL TESTING
81
4 CONCLUSION
89
5 EXPERIMENTAL PART
95
5.1 PREPARATION OF (+)-METHYL-6-0-(DIMETHYL-1,1,2-TRIMETHYPROPYL-SILYL)-
A-D-GLUCOPYRANOSIDE
(83A)
97
5.2 PREPARATION OF METHYL-2,3-ANHYDRO-6-0-(DIMETHYL-1,1,2-
TRIMETHYPROPYL-SILYL)-A-D-ALLOPYRANOSIDE
(84C)
AND ITS ISOMERS
84A, B
AND
D
98
V
5.3 PREPARATION OF (+)-(2'S, 5'S)-3-E-[5
'-(DIMETHYL-1,1,2-TRIMETHYPROPYL-
SILYLOXY)-METHYL)-2 '-METHOXY-2', 5 '-DIHYDROFURAN-4-YL]-ACRYLIC ACID
ETHYLESTER (86) IN A ONE-POT PROCEDURE 99
5.4 3-E-[2 '-((DIMETHYL-1,1,2-TRIMETHYPROPYL-SILYLOXY)-METHYL)-3 '-YL]-
ACRYLIC ACID ETHYLESTER (86A) 100
5.5 PREPARATION OF DIIRONNONACARBONYL (162) 100
5.6 PREPARATION OF (-)-ENDO-[2,3,3',4'-N-(2'S, 5'S)-3--(5'-(DIMETHYL-
1.1.2- TRIMETHYPROPYL-SILYLOXY)-METHYL)-2'-METHOXY-2',5'-DIHYDROFURAN-
4-YL)-ACRYLIC ACID DIETHYLESTERJ-IRONTRICARBONYL COMPLEX (ENDO-87)
AND ITS EPIMERIC ISOMER EXO-87 101
5.7 PREPARATION OF 4-AMINO-2,4-BISTRIMETHYLSILYLOXY-PYRIMIDINE (89) 102
5.8 PREPARATION OF AXO-[2',2"
13'13"- H -(3'-(3'"(E)-ACRYLIC ACID ETHYLESTER-
3-YL)-2', 3'-DIDEHYDRO-2' ,3 '-DIDEOXY-5 '-0-(DIMETHY I-
1.1.2- TRIMETHYPROPYLSILYL)-N-D-CYTIDINE]-IRONTRICARBONYI COMPLEX (90)
103
5.9 PREPARATION OF 3-TRIMETHYLSILYL-2-PROPYN-1-OL (120) 104
5.10 PREPARATION OF 3-TRIMETHYLSILYL-2-PROPYN-1 -AL (116B) 105
5.11 PREPARATION OF 3,3-DIALLYLOXY-L-PROPINYLTRIMETHYLSILANE (106B) 106
5.12 PREPARATION OF 1,1 -DIALLYLOXY-2-PROPYNE (106A) 107
5.13 PREPARATION OF 2,3-DIBROMO-1,1-DIETHOXYPROPANE (118) 108
5.14 PREPARATION OF 1,1-DIETHOXY-2-PROPYNE (119) 108
5.15 PREPARATION OF 1,1 -DIALLYLOXY-2-PROPYNE (106A) 109
5.16 PREPARATION OF RAC-8-ALLYLOXY-2-TRIMETHYLSILYL-7-OXO-[3.3.0]-
BICYCLOOCT-1 -ENE-3/ONE (105B) 110
5.17 PREPARATION OF RAC-8-ALLYLOXY-7-OXO-[3.3.0]-BICYCLOOCT-1-ENE-
3-ONE(105A) 112
5.18 PREPARATION OF (S)-1 -BENZYL-PYRROLIDINE-2-CARBOXYLIC ACID BENZYL
ESTER (164) ' 113
5.19 PREPARATION OF (S)-1 -BENZYL-2-(1 -HYDROXY-1,1 -DIPHENYLMETHYL)-
PYRROLIDINE (165) 113
5.20 PREPARATION OF (S)-2-(1-HYDROXY-1,1-DIPHENYLMETHYL)-PYRROLIDINE
(166) 114
5.21 PREPARATION OF (
S)-CBS-CATALYSTS
(133A-C) 115
5.22 CBS-KINETIC RESOLUTION - PREPARATION OF KETONE (-)-105B IN
ENANTIOMERICALLY PURE FORM 116
5.23 OXIDATION OF ALCOHOL (+)-130 117
VI
5.24 REPEATED CBS-KINETIC RESOLUTION - PREPARATION OF KETONE
(+)-105B
IN ENANTIOMERICALLY PURE FORM 117
5.25 PREPARATION OF (-)-(3R, 5S, 8R)-8-ALLYLOXY-2-TRIMETHYLSILYL-
7-OXO-[3.3.0]-
BICYCLOOCT-1 -ENE-3-OL (1
30)
118
5.26 PREPARATION OF (+)-(3S, 5
R,
8S)-8-ALLYLOXY-2-TRIMETHYLSILYL- 7-OXO-[3.3.0]-
BICYCIOOCT-1-ENE-3-OL
(130)
120
5.27 PREPARATION OF (+)-(1S, 2S, 5
R,
7S)-2-ALLYLOXY-3-OXO-[3.3.0]-BICYCLOOCTANE-
7-OL
(131)
120
5.28 PREPARATION OF (-)-(3
R,
5S, 8R)-8-ALLYLOXY-7-OXO-[3.3.0]- BICYCLOOCT-
1-ENE-3-OL
(132)
121
5.29 PREPARATION OF (+)-(3S, 5
R,
8S)-8-ALLYLOXY-7-OXO-[3.3.0J-BICYCLOOCT-
1- ENE-3-OL
(132)
123
5.30 PREPARATION OF (-)-(2S, 3
'R, 5'S, 8'R)-3,3,3-TRIFLUORO-2-METHOXY-2-PHENYL-
PROPIONIC ACID (8'-ALLYLOXY-2'-TRIMETHYLSILYL-7'-OXO-[3.3.0]-BICYCLOOCT-
1 '-ENE-3'-YI) ESTER
(148)
123
5.31 PREPARATION OF (+)-(2S, 3'S, 5
'R, 8'S)-3,3,3-TRIFLUORO-2-METHOXY-2-PHENYL-
PROPIONIC ACID (8'-ALLYLOXY-2'-TRIMETHYLSILYL-7'-OXO-[3.3.0]-BICYCLOOCT-
1 '-ENE-3'-YL) ESTER
(150)
125
5.32 PREPARATION OF (-)-(2S, 3'R, 5'S, 8'R)-3,3,3-TRIFLUORO-2-METHOXY-
2- PHENYL-PROPIONIC ACID (8'-ALLYLOXY-7'-OXO-[3.3.0]-BICYCLOOCT-
1 '-ENE-3'-YL) ESTER
(149)
126
5.33 PREPARATION OF (+)-(2S, 3'S,
5'R, 8'S)-3,3,3-TRIFLUORO-2-METHOXY-2-PHEN^L-
PROPIONIC ACID (8'-ALLYLOXY-7'-OXO-[3.3.0]-BICYCLOOCT-
1 '-ENE-3'-YL) ESTER
(151)
127
5.34 PREPARATION OF (-)-(3
R,
5S, 8R)-ACETIC ACID 8-ALLYLOXY-7-OXO-[3.3.0]-
BICYCLOOCT-1-ENE-3-YL ESTER
(114A)
128
5.35 PREPARATION OF (+)-(3S, 5
R,
8S)-ACETIC ACID 8-ALLYLOXY-7-OXO-[3.3.0]-
BICYCLOOCT-1 -ENE-3-YL ESTER
(114A)
129
5.36 PREPARATION OF
RAC-(3R, 5S, 8R)-ACETIC ACID 8-ALLYLOXY-7-OXO-[3.3.0]-
BICYCLOOCT-1 -ENE-3-YL ESTER (11
4B)
129
5.37
RAC-(3R, 5S)-3-HYDROXY-5-HYDROXYMETHYL-2-TRIMETHYLSILYL-CYCLOPENT-
1-ENE-CARBALDEHYDE
(157A)
134
5.38
RAC-(3R, 5S)-3-HYDROXY-5-HYDROXYMETHYL- CYCLOPENT-
1-ENE-CARBALDEHYDE
(157B)
134
VH
5.39 (-)-(3
R, 5S)-3-ACETOXY-5-HYDROXYMETHYL- CYCLOPENT-
1 -ENE-CARBALDEHYDE
(158) 135
5.40 PREPARATION OF A/-(9-ACETYL-6-OXO-6,9-DIHYDRO-1 H-PURIN-2-YL)-
ACETAMIDE (168) 136
5.41 PREPARATION OF DIPHENYL-CARBAMIC ACID 2-ACETYLAMINO- 9H-PURIN-
6-YL ESTER (156C) 136
PD-CATALYZED INTRODUCTION OF NUCLEOBASES
138
PROTOCOL A
13
G
PROTOCOLS
139
5.42 PREPARATION OF (-)-(3
'R, 5'S, 8'H)-1 -(8'-ALLYLOXY-7'-OX-[3.3.0]-
BICYCLOOCT-1 '-ENE-3'-YL)-1 /-/-PYRIMIDINE-2,4-DIONE
(100A)
139
5.43
PREPARATION OF (+)-(3'S, 5 R, 8'S)-1-(8'-ALLYLOXY-7'-OXO-[3.3.0]-
BICYCLOOCT-1 '-ENE-3'-YL)-1 /-/-PYRIMIDINE-2,4-DIONE (100A)
140
5.44
PREPARATION OF (-)-(3'R, 5'S, 8'F?)-1-(8'-ALLYLOXY-7'-OXO-[3.3.0]-
BICYCLOOCT-1 '-ENE-3'-YL)-5-FLUORO-1/-/-PYRIMIDINE-2,4-DIONE (100B)
140
5.45
PREPARATION OF (+)-(3'S, 5 R, 8'S)-1-(8'-ALLYLOXY-7'-OXO-[3.3.0]-
BICYCLOOCT-1 '-ENE-3'-YL)-5-FLUORO-1 H-PYRIMIDINE-2,4-DIONE (100B) 141
5.46
PREPARATION OF (-)-(3'R, 5'S, 8'H)-1-(8'-ALLYLOXY-7'-OXO-[3.3.0]-
BICYCLOOCT-1 '-ENE- 3'-YL)-5-BROMO-1 H-PYRIMIDINE-2,4-DIONE (100C) 141
5.47
PREPARATION OF (+)-(3'S, 5'R, 8'S)-1 -(8'-ALLYLOXY-7'-OXO-[3.3.03-
BICYCLOOCT-1 '-ENE-3'-YL)-5-BROMO-1 H-PYRIMIDINE-2,4-DIONE
(100C)
142
5.48
PREPARATION OF (-)-(3'R, 5'S, 8'H)-1-(8'-ALIYLOXY-7'-OXO-[3.3.0]-
BICYCLOOCT-1 '-ENE-3'-YL)-5-METHYL-1 H-PYRIMIDINE-2,4-DIONE
(1 OOD)
143
5.49
PREPARATION OF (+)-(3'S, 5'R, 8'S)-1-(8'-ALLYLOXY-7'-OXB-[3.3.0]-
BICYCLOOCT-1 '-ENE-3'-YL)-5-METHYL-1 H-PYRIMIDINE-2,4-DIONE
(100D)
144
5.50
PREPARATION OF (-)-(3'R, 5'S, 8'H)-A/-[1-(8'-ALLYLOXY-7'-OXO-[3.3.0]-
BICYCLOOCT-1 '-ENE-3'-YL)-2-OXO-1,2-DIHYDRO-PYRIMIDIN-4-YL]-
BENZAMIDE (100E) 144
5.51
PREPARATION OF (+)-(3'S, 5'R, 8'S)-/S/-[1-(8'-ALLYLOXY-7'-OXO-[3.3.0]-
BICYCLOOCT-1 '-ENE-3'-YL)-2-OXO-1,2-DIHYDRO-PYRIMIDIN-4-YL]-
BENZAMIDE (100E) 145
VIII
5.52 PREPARATION OF (-)-(3
'R, 5'S,
8
'A?)-DIPHENYL-CARBAMIC ACID
2-ACETYLAMINO-9-(8 '-ALLYLOXY-7 '-OXO-[3.3.0]-BICYCLOOCT-1 '-ENE-
3 '-YL)-9H-PURIN-6-YL ESTER (1 OOF) 145
5.53 PREPARATION OF (+)-(3'S,
5'R,
8
'S)-DIPHENYL-CARBAMIC ACID
2-ACETYLAMINO-9-(8'-ALLYLOXY-7'-OXO-[3.3.0]-BICYCLOOCT-R-ENE-
3 '-YL)-9H-PURIN-6-YL ESTER (1 OOF) 146
5.54 PREPARATION OF (-)-(3
'R, 5'S,
8
'R)-9-(8'-ALLYLOXY-7'-OXO-[3.3.0]-
BICYCLOOCT-1 '-ENE-3 '-YL)-9H-PURIN-6-YLAMINE (1 OOG) 146
5.55 PREPARATION OF (+)-(3'S, 5
'R, 8'S)-9-(8'-ALLYLOXY-7'-OXO-[3.3.0]-
BICYCLOOCT-1 '-ENE-3'-YL)-9H-PURIN-6-YLAMINE (1 OOG) 147
GENERAL PROCEDURE FOR ONE-POT HYDROLYSIS AND SILYLATION
148
5.56 PREPARATION OF (+)-(3
R, 5S)-5-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXY]-3-(2' ,4 '-DIOXO-3 ',4 '-DIHYDRO-2/-/-PYRIMIDIN-1 '-YL)~
CYCLOPENT-1 -ENECARBALDEHYDE
(95A)
149
5.57 PREPARATION OF (-)-(3S, 5R)-5-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXY]-3-(2',4'-DIOXO-3',4'-DIHYDRO-2H-PYRIMIDIN-1'-YL)-
CYCLOPENT-1-ENECARBALDEHYDE
(95A)
150
5.58 PREPARATION OF (+)-(3
R, 5S)-3-(5'-FLUORO-2',4'-DIOXO- 3',4'-DIHYDRO-
2H-PYRIMIDIN-1 '-YL)-5-[DIMETHYL-(1,
1
,2-TRIMETHYL-PROPYL)-SILANYLOXY]-
CYCLOPENT-1-ENECARBALDEHYDE
(95B)
150
5.59 PREPARATION OF (-)-(3S, 5F?)-3-(5'-FLUORO-2',4'-DIOXO-
3',4'-DIHYDRO-
2H-PYRIMIDIN-1 '-YL)-5-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXY]-
CYCLOPENT-1 -ENECARBALDEHYDE
(95B) 151
5.60 PREPARATION OF (+)-(3R 5S)-3-(5'-BROMO-2',4'-DIOXO-3',4'-DIHYDRO-
2
H-PYRIMIDIN
-1
'-YL)-5-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXY]-
CYCLOPENT-1 -ENECARBALDEHYDE
(95C) 151
5.61 PREPARATION OF (-)-(3S, 5F?)-3-(5'-BROMO-2',4'-DIOXO-
3',4'-DIHYDRO-
2H-PYRIMIDIN-1 '-YL)-5-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXY]-
CYCLOPENT-1-ENECARBALDEHYDE
(95C)
152
5.62 PREPARATION OF (+)-(3
R, 5S)-5-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXY]-3-(5'-METHYL-2'I4'-DIOXO-3',4'-DIHYDRO-2H-PYRIMIDIN-
1 '-YL)-CYCLOPENT
-1
-ENECARBALDEHYDE
(95D) 152
DC
5.63 PREPARATION OF (-)-(3S, 5R)-5-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXY]-3-(5'-METHYL-2' ,4'-DIOXO-3' ,4 '-DIHYDRO- 2/-/-PYRIMIDIN-
1 -YL)-CYCLOPENT-1 -ENECARBALDEHYDE
(95D)
153
5.64 PREPARATION OF (+)-(3
R, 5S)-A/-( 1 -{4-[DIMETHYL-( 1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXY]-3-FORMYL-CYCLOPENT-2-ENYL}-2'-OXO-R,2'-DIHYDRO-PYRIMIDIN-
4 '-YL)-BENZAMIDE
(95E)
154
5.65 PREPARATION OF (-)-(3S,
5R)-N-( 1 -{4-[DIMETHYL-( 1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXY]-3-FORMYL-CYCLOPENT-2-ENYL}-2'-OXO-1',2'-DIHYDRO-PYRIMIDIN-
4'-YL)-BENZAMIDE
(95E)
155
5.66 PREPARATION OF (+)-(3
R, 5S)-DIPHENYL-CARBAMIC ACID 2'-ACETYLAMINO-
9'-{4-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXY]- 3-FORMYL-
CYCLOPENT-2-ENYL}-9H-PURIN-6'-YL ESTER
(95F)
155
5.67 PREPARATION OF (-)-(3S, 5R)-DIPHENYL-CARBAMJC ACID 2'-ACETYLAMINO-
9'-{4-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXY]-3-FORMYL-
CYCLOPENT-2-ENYL}-9H-PURIN- 6'-YL ESTER
(95F)
156
5.68 PREPARATION OF (+)-(3
R, 5S)-3-(6'-AMINO-PURIN-9'-YL)- 5-DIMETHYL-(1,1,2-
TRIMETHYL-PROPYL)-SILANYLOXY]-CYCLOPENT-1 -ENECARBALDEHYDE
(95G)
156
5.69 PREPARATION OF (-)-(3S, 5F?)-3-(6'-AMINO-PURIN-9'-YL)-
5-[DIMETHYL-(1,1,2-
TRIMETHYL-PROPYL)-SILANYLOXY]- CYCLOPENT-1 -ENECARBALDEHYDE
(95G)
157
5.70 PREPARATION OF (+)-(3
R, 5S)-3-(5'-FLUORO-2',4'-DIOXO- 3',4'-DIHYDRO-
2H-PYRIMIDIN-R-YL)-5-(TERT-BUTYL-DIPHENYL-SILANYLOXYMETHYL)-
CYCLOPENT-1 -ENECARBALDEHYDE
(155A)
157
5.71 PREPARATION OF (+)-(3
R, 5S)-3-(5'-BROMO-2',4'-DIOXO- 3',4'-DIHYDRO-
2H-PYRIMIDIN-1'-YL)-5-(TERF-BUTYL-DIPHENYL-SILANYLOXYMETHYL)-
CYCLOPENT-1-ENECARBALDEHYDE
(155B)
158
5.72 PREPARATION OF (+)-(3R, 5S)-A/-{1-[4-(FE/F-BUTYL-DIPHENYL-
SILANYLOXYMETHYL)-3-FORMYL-CYCLOPENT-2-ENY|J-2 -OXO-1 ',2'-DIHYDRO-
PYRIMIDIN-4'-YL}-BENZAMIDE
(155C)
159
5.73 PREPARATION OF (+)-(3
R, 5S)-DIPHENYL-CARBAMIC ACID 2'-ACETYLAMINO-
9 '-[4-(FERF-BUTYL-DIPHENYL-SILANYLOXYMETHYL)- 3-FORMYL-
CYCLOPENT-2-ENYL]-9H-PURIN-6'-YL ESTER
(155D)
160
X
GENERAL PROCEDURE FOR THE REDUCTION OF ALDEHYDES
95
AND
155 161
5.74 PREPARATION OF (-)-(3
R, 5S)-1 '-{4-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-3-HYDROXYMETHYL-CYCLOPENT-2-ENYL}-1/7-PYRIMIDINE-
2',4'-DIONE
(113A)
161
5.75 PREPARATION OF (+)-(3S, 5F?)-1
'-{4-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYNRIETHYL]-3-HYDROXYMETHYL-CYCLOPENT-2-ENYL}-1H-PYRIMIDINE-
2',4'-DIONE
(113A)
162
5.76 PREPARATION OF (+)-(3S, 5/?)-5'-FLUORO-1
'-{4-[DIMETHYL-(1,1,2-TRIMETHYL-
PROPYL)-SILANYLOXYMETHYL]-3-HYDROXYMETHYL-CYCLOPENT-2-ENYL}-
1H-PYRIMIDINE-2',4'-DIONE
(113B)
162
5.77 PREPARATION OF (-)-(3
R, 5S)-5'-FLUORO-1 '-{4-[DIMETHYL-(1,1,2-TRIMETHYL-
PROPYL)-SILANYLOXYMETHYL]-3-HYDROXYMETHYL-CYCLOPENT- 2-ENYL}-
1W-PYRIMIDINE-2',4'-DIONE
(113B)
163
5.78 PREPARATION OF (-)-(3
R, 5S)-5'-BROMO-1 '-{4-[DIMETHYL-(1,1,2-TRIMETHYL-
PROPYL)-SILANYLOXYMETHYL]-3-HYDROXYMETHYL-CYCLOPENT-2-ENYL}-
1
/-/-PYRIMIDINE-2',4'-DIONE
(113C)
164
5.79 PREPARATION OF (+)-(3S, 5F?)-5'-BROMO-1
'-{4-[DIMETHYL-(1,1,2-TRIMETHYL-
PROPYL)-SILANYLOXYMETHYL]-3-HYDROXYMETHYL-CYCLOPENT- 2-ENYL}-
1H-PYRIMIDINE-2',4'-DIONE
(113C)
165
5.80
RAC-(3S, 5R)-5'-BROMO-1 '-{3-DIMETHOXYMETHYL- 4-[DIMETHYL-
(1,1
12-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-CYCLOPENT-2-ENYL}-
1H-PYRIMIDINE-2',4'-DIONE
(160)
165
5.81 PREPARATION OF (-)-(3
R, 5S)-1 '-{4-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-3-HYDROXYMETHYL-CYCLOPENT-2-ENYL}-5'-METHYL-
1
/-/-PYRIMIDINE-2',4'-DIONE
(113D)
166
5.82 PREPARATION OF (+)-(3S, 5/?)-1
'-{4-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-3-HYDROXYMETHYL-CYCLOPENT-2-ENYL}- 5 '-METHYL-
1H-PYRIMIDINE-2',4'-DIONE
(113D)
167
5.83 PREPARATION OF (+)-(3S, 5/?)-A/-(1
'-{4-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-3-HYDROXYMETHYL-CYCLOPENT-2-ENYL}-2'-OXO-
1',2'-DIHYDRO-PYRIMIDIN-4'-YL)-BENZAMIDE
(113E-1)
167
5.84 PREPARATION OF (-)-(3
R, 5S)-A/-(1 '-{4-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-3-HYDROXYMETHYL-CYCLOPENT-2-ENYL}-2'-OXO-
1',2'-DIHYDRO-PYRIMIDIN-4'-YL)-BENZAMIDE
(113E-1)
168
XI
5.85 PREPARATION OF (+M3
R, 5S)-4'-AMINO-1 '-{4-[DIMETHYL-
(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-3-HYDROXYMETHYL-
CYCLOPENT-2-ENYL}~1 H-PYRIMIDIN-2'-ONE (11
3E)
168
5.86 PREPARATION OF (-)-(3S, 5R)-4 '-AMINO-1 '-{4-[DIMETHYL-
(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-3-HYDROXYMETHYL-
CYCLOPENT-2-ENYL}-1 H-PYRIMIDIN-2'-ONE
(113E)
169
5.87 PREPARATION OF (-)-(3
R, 5S)-2'-AMINO-9'-{4-[DIMETHYL-(1,1,2-TRIMETHYL-
PROPYL)-SILANYLOXYMETHYL]-3-HYDROXYMETHYL-CYDOPENT-2-ENYL}-
1',9'-DIHYDRO-PURIN-6'-ONE
(113F)
170
5.88 PREPARATION OF (+)-(3S,
5FT)-2'-AMINO-9'-(4-[DIMETHYL-(1,1,2-TRIMETHYL-
PROPYL)-SILANYLOXYMETHYL]-3-HYDROXYMETHYL-CYCLOPENT-2-ENYL}-
1',9'-DIHYDRO-PURIN-6'-ONE
(113F)
171
5.89 PREPARATION OF (-)-(3R 5S)-{1-(6'-AMINO-PURIN-9'-YL)-4-[DIMETHYL-
(1,1 ^-TRIMETHYL-PROPYO-SILANYLOXYMETHYLL-CYCLOPENT-^ENE-S-YL}-
METHANOL (113G) 171
5.90 PREPARATION OF (+)-(3S, 5R)-{1-(6'-AMINO-PURIN-9'-YL)-4-[DIMETHYL-
(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-CYCLOPENT-2-ENE-3-YL}-
METHANOL (113G) 172
5.91 PREPARATION OF (-)-(3
R, 5S)-5'-FLUORO-1 '-[4-(FERT-BUTYL-DIPHENYL-
SILANYLOXYMETHYL)-3-HYDROXYMETHYL-CYCLOPENT-2-ENYL]-
1H-PYRIMIDINE-2',4'-DIONE
(159A)
173
5.92 PREPARATION OF (+)-(3
R, 5S)-5'-BROMO-1 '-[4-(TERT-BUTYL-DIPHENYL-
SILANYLOXYMETHYL)-3-HYDROXYMETHYL-CYCLOPENT-2-ENYL]-
1H-PYRIMIDINE-2',4'-DIONE
(159B)
174
5.93 PREPARATION OF (-)-(3S, 5R)-/V-{1 '-[4-(TERF-BUTYL-DIPHENYL-
SILANYLOXYMETHYL)-3-HYDROXYMETHYL-CYCLOPENT-2-ENYL]-2'-OXO-
1 ',2'-DIHYDRO-PYRIMIDIN-4'-YL}-BENZAMIDE
(159C-1)
175
5.94 PREPARATION OF (-)-(3S,
5R)- 4'-AMINO-1 '-[4-(FERT-BUTYI-DIPHENYL-
SILANYLOXYMETHYL)-3-HYDROXYMETHYL-CYCLOPENT-2-ENY!]-
1H-PYRIMIDIN-2'-ONE
(159C)
175
5.95 PREPARATION OF (-)-(3R, 5S)- 2'-AMINO-9'-[4-(TE/F-BUTYL-DIPHENYL-
SILANYLOXYMETHYL)-3-HYDROXYMETHYL-CYCLOPENT-2-ENYL]-
1',9'-DIHYDRO-PURIN-6'-ONE
(159D)
176
XN
DESTINATION OF THE ALCOHOLS
M-113F AND F-M13Q
177
5.96
PREPARATION OF (-)-(1 R, 4S)-2'-AMINO-9'-[3,4-BIS-(HYDROXYMETHYL)-
2-CYCLOPENTEN-1 -YL]-9H-PURINE-6-ONE (161A)
177
5.97
PREPARATION OF (-)-(1 R, 4S)-6'-AMINO-9'-[3,4-BIS-(HYDROXYMETHYL)-
2-CYCLOPENTEN-1 -YL]-9TF-PURINE (161 B) 178
GENERAL PROCEDURES FOR THE WITTLG REACTION (PREPARATION OF
93A-I)
179
METHOD A (WITTIG REACTION)
179
METHOD B (HORNER-EMMONS MODIFICATION)
180
5.98 PREPARATION OF (-)-(3'R,
5'S)-E-3-{5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-3 '-(2'' ,4' '-DIOXO-3",4' '-DIHYDRO-2/-/-PYRIMIDIN-
1
' '-YL)-CYCLOPENT-1 '-ENYL}-ACRYLIC ACID ETHYL ESTER
(93A)
180
5.99 PREPARATION OF (+)-(3'S, 5 'R)-E-3-[5'-[DIMETHYL-(
1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-3 '-(2 " ,4' '-DIOXO-3'' ,4' '-DIHYDRO-2H-PYRIMIDIN-
1
' '-YL)-CYCLOPENT-1 '-ENYL]-ACRYLIC ACID ETHYL ESTER
(93A)
181
5.100 PREPARATION OF (-)-(3
'R, 5'S)--3-[3'-(5''-FLUORO-2'',4''-DIOXO-3",4' -
DIHYDRO2H-PYRIMIDIN-1 "-YL)-5 '-[DIMETHYL-( 1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYLJ-CYCLOPENT
1
'-ENYL]-ACRYLIC ACID ETHYL ESTER
(93B)
181
5.101 PREPARATION OF (+)-(3'S, 5'
R)-E-3-[3'-(5''-FLUORO-2'',4''-DIOXO-3'',4"-
DIHYDRO-2H-PYRIMIDIN-1 ''-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYL]-ACRYLIC ACID ETHYL ESTER
(93B)
183
5.102 PREPARATION OF (-)-(3'R,
5'S)--3-[3'-(5''-BROMO-2'',4''-DIOXO-3'',4"-
DIHYDRO-2H-PYRIMIDIN-1 "-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYL]-ACRYLIC ACID ETHYL ESTER (93C) 183
5.103 PREPARATION OF (+)-(3'S, 5'R)-E-3-[3'-(5''-BROMO-2",4''-DIOXO-3",4
DIHYDRO-2H-PYRIMIDIN-1 ''-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYL}-ACRYLIC ACID ETHYL ESTER
(93C)
184
5.104 PREPARATION OF (-)-(3
'R, 5'S)--3-[5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-3'-(5''-METHYL-2'',4''-DIOXO-3'',4''-DIHYDRO-2H-
PYRIMIDIN-1 "-YL)- CYCLOPENT-1 '-ENYL]-ACRYLIC ACID ETHYL ESTER
(93D)
184
XM
5.105 PREPARATION OF (+)-(3'S,
5'R)-E-3-[5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-3 '-(5' '-METHYL-2" ,4"-DIOXO-3 ",4' '-DIHYDRO-2H-
PYRIMIDIN-1' '-YL)- CYCLOPENT-1 '-ENYL]-ACRYLIC ACID ETHYL ESTER
(93D)
185
5.106 PREPARATION OF (-)-(3'R 5'S)--3-[3'-(4''-BENZOYLAMINO-2'-OXO-2H-
PYRIMIDIN-1 "-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYLJ-CYDOPENT-1 '-ENYL]-ACRYLIC ACID ETHYL ESTER
(93E-1
) 186
5.107 PREPARATION OF (+)-(3'S, 5'
R)-E-3-[3'-(4''-BENZOYLAMINO-2''-OXO-2H-
PYRIMIDIN-1 "-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYL]-ACRYLIC ACID ETHYL ESTER
(93E-1) 1
87
5.108 PREPARATION OF (-)-(3
'R, 5'S)-E-3-{3'-(2"-ACETYLAMINO-6"-
DIPHENYLCARBAMOYLOXY-PURIN-9"-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYLJ-ACRYLIC ACID ETHYL ESTER
(93F-1) 1
87
5.109 PREPARATION OF (+)-(3'S,
5'R)-E-3-{3'-(2''-ACETYLAMINO-6"-
DIPHENYLCARBAMOYLOXY-PURIN-9"-YL)-5'-[DIMETHYL-(T,
172-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYL}- ACRYLIC ACID ETHYL ESTER
(93F-1)
188
5.110 PREPARATION OF (-)-(3
'R, 5'S)-E-3-{3'-(6"-AMINO-PURIN-9"-YL)-
5 '-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-CYCLOPENT-
1 '-ENYL}-ACRYIIC ACID ETHYL ESTER (93G) 188
5.111 PREPARATION OF (+)-(3'S, 5'R)-E-3-{3'-(6"-AMINO-PURIN-9"-YL)-
5'-[DIMETHYL-(1
I1,2-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-CYCLOPENT-
1 '-ENYLJ-ACRYLIC ACID ETHYL ESTER (93G) 189
5.112 PREPARATION OF (-)-(1'R 4'S)-A/-(1-{4'-[DIMETHYL-(1,1,2-TRIMETHYL-
PROPYL)-SILANYLOXYMETHYL]-3'-VINYL-CYCLOPENT-2'-ENE-1'-YLJ-2-OXO-
1,2-DIHYDRO-PYRIMIDIN-4-YL)-BENZAMIDE
(93H-1
) 190
5.113 PREPARATION OF (-)-(3
'R, 5'S)-E-3-{3'-(2"-AMINO-6"-OXO-
1' ',6"-DIHYDRO-PURIN-9"-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYLJ-ACRYLIC ACID ETHYL ESTER
(93F) 191
5.114 PREPARATION OF (+)-(3'S,
5'R)-E-3-{3'-(2"-AMINO-6"-OXO-
1 ",6"-DIHYDRO-PURIN-9"-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYLJ-ACRYLIC ACID ETHYL ESTER
(93F)
192
5.115 PREPARATION OF (-)-(3
'R, 5' S)-E-3-{3 '-(4"-AMINO-2' '-OXO-2H-PYRIMIDIN-
1 "-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-
CYCLOPENT-1 -ENYLJ-ACRYLIC ACID ETHYL ESTER
(93E)
192
5.116 PREPARATION OF (+)-(3'S,
5'R)-E-3-{3'-(4"-AMINO-2"-OXO-2H-PYRIMIDIN-
1 "-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-
CYCLOPENT-1 '-ENYLJ-ACRYLIC ACID ETHYL ESTER
(93E)
193
XIV
5.117 PREPARATION OF (-)-(3'R, 5'S)-4'-AMINO-1
'-{5-[DIMETHYL-(1,1,2-TRIMETHYL-
PROPYL)-SILANYLOXYMETHYL]-1 -VINYL-1 -CYCLOPENTENE-3-YLJ-
1 H-PYRIMIDIN-2-ONE (93H) 193
5.118
RAC-(3'RS, 5'RS)-E-3-[3'-(5"-BROMO-2'',4"-DIOXO-3",4"-DIHYDRO-
2H-PYRIMIDIN-1' '-YL)-5'-(TE/F-BUTYL-DIPHENYL-SILANYLOXYMETHYL)-
CYCLOPENT-1 '-ENYLJ-ACRYLIC ACID ETHYL ESTER (93I) 194
GENERAL PROCEDURE FOR THE COMPLEXATION OF DIENES 93
195
5.119 PREPARATION OF (-)-EXO- AND (+)-ENDO-(3'R 5'S)-E-3-{5'-[DIMETHYL-
(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-3'-(2",4"-DIOXO-
3' ',4' '-DIHYDRO-2H-PYRIMIDIN-1 "-YL)- CYCLOPENT-1 '-ENYLJ-
ACRYLIC ACID ETHYL ESTER-IRONTRICARBONYL COMPLEX (91A) 196
5.120 PREPARATION OF (+)-EXO- AND (-)-ENDO-E-(3'S,
5'FL)-E-3-{5'-[DIMETHYL-
(1.1,2-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-3'-(2",4"-DIOXO-
3",4"-DIHYDRO-2H-PYRIMIDIN-1 "-YL)-CYCLOPENT-1 '-ENYLJ-
ACRYLIC ACID ETHYL ESTER-IRONTRICARBONYL COMPLEX (91A) 197
5.121 PREPARATION OF (-)-EXO- AND (+)-ENDO-(3
'R, 5'S)-E-3-{3 '-(5' '-FLUORO-
2'' ,4' '-DIOXO-3'' ,4"-DIHYDRO-2H-PYRIMIDIN-1' '-YL)-5 '-[DIMETHYL-
(1,1,
2
-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-CYCLOPENT
-1
-ENYLJ-
ACRYLIC ACID ETHYL ESTER-IRONTRICARBONYL COMPLEX (91B) 198
5.122 PREPARATION OF (+)-EXO- AND (-)-ENDO-(3'S,
5'E)-E-3-{3'-(5'-FLUORO-
2 " ,4' '-DIOXO-3 " ,4' '-DIHYDRO-2H-PYRIMIDIN-1' '-YL)-5 '-[DIMETHYL-
(1,1,
2
-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-CYCLOPENT
-1
-ENYLJ-
ACRYLIC ACID ETHYL ESTER-IRONTRICARBONYL COMPLEX (91B) 199
5.123 PREPARATION OF (-)-EXO- AND (+)-E/TDO-(3'R,
5'S)-E-3-{3'-(5"-BROMO-
2 " ,4' '-DIOXO-3'' ,4' '-DIHYDRO-2H-PYRIMIDIN-1' '-YL)-5'-[DIMETHYL-
(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYLJ-
ACRYLIC ACID ETHYL ESTER-IRONTRICARBONYL COMPLEX (91C) 200
5.124 PREPARATION OF (+)-EXO- AND (-)-ENDO-(3'S,
5'F?)-E-3-{3'-(5"-BROMO-
2 " ,4' '-DIOXO-3",4' '-DIHYDRO-2H-PYRIMIDIN-1' '-YL)-5 '-[DIMETHYL-
(1,1,
2
-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-CYCLOPENT
-1
'-ENYLJ-
ACRYLIC ACID ETHYL ESTER-IRONTRICARBONYL COMPLEX (91C) 202
5.125 PREPARATION OF (-)-EXO- AND (+)-ENDO-(3'F?,
5'S)-E-3-{5'-[DIMETHYL-
(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-3 '-(5' -METHYL-2 " ,4'
'-DIOXO-
XV
3",4''-DIHYDRO-2H-PYRIMIDIN-1 "-YL)-CYCLOPENT-1 '-ENYLJ-
ACRYLIC-ACID ETHY! ESTER-IRONTRICARBONYL COMPLEX (91 D) 202
5.126 PREPARATION OF (+)-RO- AND (-)-ENCTO-(3'S,
5'R)-E-3-{5'-[DIMETHYL-
(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-3 '-(5' '-METHYL-2 ",4'
'-DIOXO-
3",4"-DIHYDRO-2H-PYRIMIDIN-1 "-YL)- CYCLOPENT-1 '-ENYLJ-
ACRYLIC ACID ETHYL ESTER-IRONTRICARBONYL COMPLEX (91 D) 204
5.127 PREPARATION OF (-)-AXO-(3' S, 5
'R)-E-3-[3 '-(4' '-BENZOYLAMINO-
2' '-OXO-2W-PYRIMIDIN-1 "-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYL]-ACRYLIC ACID
ETHYL ESTER-IRONTRICARBONYL COMPLEX (91E-1) 204
5.128 PREPARATION OF
(-)-EXO-(3'R, 5'S)-E-3-{3'-(4''-AMINO-2'-OXO-
2H-PYRIMIDIN-1' '-YL)-5 '-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYLJ-ACRYLIC ACID
ETHYL ESTER-IRONTRICARBONYL COMPLEX (91 E) - 205
5.129 PREPARATION OF (+)-AXO-(3' S, 5 'F?)-E-3-{3 '-(4' '-AMINO-2' -OXO-
2H-PYRIMIDIN-1 "-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYLJ-ACRYLIC ACID ETHYL ESTER-
IRONTRICARBONYL COMPLEX (91 E) 206
5.130 PREPARATION OF (-)-EXO- AND (+)-ENEFO-(3'R,
5'S)-E-3-{3'-(4''-AMINO-
2"-OXO-2H-PYRIMIDIN-1 "-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYLJ-ACRYLIC ACID ETHYL ESTER-
IRONTRICARBONYL COMPLEX (91 F) 207
5.131 PREPARATION OF (+)-EXO-(3' S, 5
'R)-E-3-{3 '-(4' '-AMINO-2' '-OXO-
2/-/-PYRIMIDIN-1' '-YL)-5'-[DIMETHYL-( 1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYLJ-ACRYLIC ACID ETHYL ESTER-
IRONTRICARBONYL COMPLEX (91
F)
208
5.132 PREPARATION OF (-)-EJRO-(3'R
I 5'S)-E-3-{3'-(4''-ACETAMINO-2''-OXO-
2H-PYRIMIDIN-1 ''-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-
SILANYLOXYMETHYL]-CYCLOPENT-1 '-ENYLJ-ACRYLIC ACID ETHYL ESTER-
IRONTRICARBONYL COMPLEX (91F-1) 209
5.133 PREPARATION OF (+)-EXO- AND
ENDO-(3'R, 5'S)-E-3-{3'-(6''-AMINO-PURIN-
9"-YL)-5'-[DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-CYCLOPENT-
1 '-ENYLJ-ACRYLIC ACID ETHYL ESTER-IRONTRICARBONYL COMPLEX (91 G) 209
5.134 PREPARATION OF (+)-ENDO-(3'S, 5'R)-E-3-{3'-(6"-AMINO-
PURIN-9"-YL)-
5' [DIMETHYL-(1,1,2-TRIMETHYL-PROPYL)-SILANYLOXYMETHYL]-CYCLOPENT-1 '-
ENYLJ-ACRYLIC ACID ETHYL ESTER-IRONTRICARBONYL COMPLEX (91G) 211
XVI
5.135 PREPARATION OF
AXO-(3
R, 5S)-4'-AMINO-1 '-{5-[DIMETHYL-(1,1,2-TRIMETHYL-
PROPYL)-SILANYLOXYMETHYL]-1 -VINYL-CYCLOPENT-1 -ENE-3-YL}-1 H-PYRIMIDIN-
2-ONE-IRONTRICARBONYL COMPLEX (91 H) 211
5.136 PREPARATION OF (3
R, 5S)-4'-AMINO-1 '-{5-[DIMETHYL-(1,1,2-TRIMETHYL-
PROPYL)-SILANYLOXYMETHYL]-1-ETHYL-CYCLOPENT-1 -ENE-3-YL}-
1 H-PYRIMIDIN-2-ONE (91 H-1) 212
5.137 PREPARATION OF
RAC-EXO- AND ANDO-(3'RS, 5'SR)- 3--[3'-(5"-BROMO-
2 ",4' '-DIOXO-3" ,4' *-DIHYDRO-2H-PYRIMIDIN-1' '-YL)-5'-(TE/F-BUTYL-
DIPHENYL-SILANYLOXYMETHYL)-CYCLOPENT-1 '-ENYL]-ACRYLIC ACID
ETHYL ESTER-IRONTRICARBONYL COMPLEX (91I) 212
\
6 APPENDIX
214
7
REFERENCES
21
6 |
| any_adam_object | 1 |
| author | Velčický, Juraj |
| author_facet | Velčický, Juraj |
| author_role | aut |
| author_sort | Velčický, Juraj |
| author_variant | j v jv |
| building | Verbundindex |
| bvnumber | BV019738392 |
| ctrlnum | (OCoLC)249110502 (DE-599)BVBBV019738392 |
| discipline | Chemie / Pharmazie |
| format | Thesis Book |
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| genre | (DE-588)4113937-9 Hochschulschrift gnd-content |
| genre_facet | Hochschulschrift |
| id | DE-604.BV019738392 |
| illustrated | Illustrated |
| indexdate | 2024-11-22T17:40:42Z |
| institution | BVB |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-013065144 |
| oclc_num | 249110502 |
| open_access_boolean | |
| owner | DE-355 DE-BY-UBR |
| owner_facet | DE-355 DE-BY-UBR |
| physical | XVIII, 227 S. Ill., graph. Darst. 30 cm |
| publishDate | 2002 |
| publishDateSearch | 2002 |
| publishDateSort | 2002 |
| record_format | marc |
| spelling | Velčický, Juraj Verfasser aut Transition metal mediated, enantioselective synthesis of novel carbocyclic nucleoside analogs with strong apoptosis-inducing properties vorgelegt von Juraj Velčický 2002 XVIII, 227 S. Ill., graph. Darst. 30 cm txt rdacontent n rdamedia nc rdacarrier Köln, Univ., Diss., 2003 Carbocyclen (DE-588)4131204-1 gnd rswk-swf Asymmetrische Synthese (DE-588)4135603-2 gnd rswk-swf Pauson-Khand-Reaktion (DE-588)4384156-9 gnd rswk-swf Katalysator (DE-588)4029919-3 gnd rswk-swf Palladiumkomplexe (DE-588)4223138-3 gnd rswk-swf Nucleosidanaloga (DE-588)4257779-2 gnd rswk-swf (DE-588)4113937-9 Hochschulschrift gnd-content Nucleosidanaloga (DE-588)4257779-2 s Carbocyclen (DE-588)4131204-1 s Asymmetrische Synthese (DE-588)4135603-2 s Pauson-Khand-Reaktion (DE-588)4384156-9 s DE-604 Palladiumkomplexe (DE-588)4223138-3 s Katalysator (DE-588)4029919-3 s DNB Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=013065144&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Velčický, Juraj Transition metal mediated, enantioselective synthesis of novel carbocyclic nucleoside analogs with strong apoptosis-inducing properties Carbocyclen (DE-588)4131204-1 gnd Asymmetrische Synthese (DE-588)4135603-2 gnd Pauson-Khand-Reaktion (DE-588)4384156-9 gnd Katalysator (DE-588)4029919-3 gnd Palladiumkomplexe (DE-588)4223138-3 gnd Nucleosidanaloga (DE-588)4257779-2 gnd |
| subject_GND | (DE-588)4131204-1 (DE-588)4135603-2 (DE-588)4384156-9 (DE-588)4029919-3 (DE-588)4223138-3 (DE-588)4257779-2 (DE-588)4113937-9 |
| title | Transition metal mediated, enantioselective synthesis of novel carbocyclic nucleoside analogs with strong apoptosis-inducing properties |
| title_auth | Transition metal mediated, enantioselective synthesis of novel carbocyclic nucleoside analogs with strong apoptosis-inducing properties |
| title_exact_search | Transition metal mediated, enantioselective synthesis of novel carbocyclic nucleoside analogs with strong apoptosis-inducing properties |
| title_full | Transition metal mediated, enantioselective synthesis of novel carbocyclic nucleoside analogs with strong apoptosis-inducing properties vorgelegt von Juraj Velčický |
| title_fullStr | Transition metal mediated, enantioselective synthesis of novel carbocyclic nucleoside analogs with strong apoptosis-inducing properties vorgelegt von Juraj Velčický |
| title_full_unstemmed | Transition metal mediated, enantioselective synthesis of novel carbocyclic nucleoside analogs with strong apoptosis-inducing properties vorgelegt von Juraj Velčický |
| title_short | Transition metal mediated, enantioselective synthesis of novel carbocyclic nucleoside analogs with strong apoptosis-inducing properties |
| title_sort | transition metal mediated enantioselective synthesis of novel carbocyclic nucleoside analogs with strong apoptosis inducing properties |
| topic | Carbocyclen (DE-588)4131204-1 gnd Asymmetrische Synthese (DE-588)4135603-2 gnd Pauson-Khand-Reaktion (DE-588)4384156-9 gnd Katalysator (DE-588)4029919-3 gnd Palladiumkomplexe (DE-588)4223138-3 gnd Nucleosidanaloga (DE-588)4257779-2 gnd |
| topic_facet | Carbocyclen Asymmetrische Synthese Pauson-Khand-Reaktion Katalysator Palladiumkomplexe Nucleosidanaloga Hochschulschrift |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=013065144&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| work_keys_str_mv | AT velcickyjuraj transitionmetalmediatedenantioselectivesynthesisofnovelcarbocyclicnucleosideanalogswithstrongapoptosisinducingproperties |