N-heterocyclic carbenes: aromatic Breslow intermediates, synthesis of novel electron-deficient NHC catalysts and NHC catalysis
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| Format: | Abschlussarbeit Buch |
| Sprache: | English |
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Köln
2020
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| Beschreibung: | VI, 195 Seiten Illustrationen, Diagramme 21 cm |
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| 008 | 201012s2020 gw a||| m||| 00||| eng d | ||
| 015 | |a 20,H11 |2 dnb | ||
| 016 | 7 | |a 1217340327 |2 DE-101 | |
| 020 | |c Broschur | ||
| 035 | |a (OCoLC)1220896773 | ||
| 035 | |a (DE-599)DNB1217340327 | ||
| 040 | |a DE-604 |b ger |e rda | ||
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| 084 | |a VK 5550 |0 (DE-625)147403:253 |2 rvk | ||
| 084 | |a 540 |2 sdnb | ||
| 100 | 1 | |a Sudkaow, Panyapon |d 1990- |e Verfasser |0 (DE-588)1213488761 |4 aut | |
| 245 | 1 | 0 | |a N-heterocyclic carbenes |b aromatic Breslow intermediates, synthesis of novel electron-deficient NHC catalysts and NHC catalysis |c vorgelegt von Panyapon Sudkaow |
| 264 | 1 | |a Köln |c 2020 | |
| 300 | |a VI, 195 Seiten |b Illustrationen, Diagramme |c 21 cm | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 502 | |b Dissertation |c Universität Köln |d 2020 | ||
| 655 | 7 | |0 (DE-588)4113937-9 |a Hochschulschrift |2 gnd-content | |
| 856 | 4 | 2 | |m B:DE-101 |q application/pdf |u https://d-nb.info/1217340327/04 |3 Inhaltsverzeichnis |
| 856 | 4 | 2 | |m DNB Datenaustausch |q application/pdf |u http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=032343026&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |3 Inhaltsverzeichnis |
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| adam_text | TABLE
OF
CONTENTS
1.
SUMMARY
....................................................................................................................
1
1.1
CHARACTERIZATION
AND
REACTIVITY
OF
FIRST
BRESLOW
INTERMEDIATES
FROM
AROMATIC
N-
HETEROCYCLIC
CARBENES
....................................................................................................
1
1.2
APPLICATIONS
OF
NHC
CATALYSIS
FOR
THE
FORMATION
OF
Y-BUTYROLACTONE
FROM
ENAL
.................................................................................................................................
3
1.3
APPLICATIONS
OF
NHC
CATALYSIS
FOR
THE
FORMATION
OF
Y-LACTAMS
FROM
ENALS
.........
5
1.4
SYNTHESIS
AND
CHARACTERISATION
OF
NOVEL
ELECTRON
DEFICIENT
TRIAZOLIUM
PRECURSORS
BEARING
CEFS
GROUPS
.....................................................................................................
7
2.
INTRODUCTION
...............................................................................................................
9
3.
BACKGROUND
.............................................................................................................
10
3.1
AN
OVERVIEW
OF
CARBENE
........................................................................................
10
3.2
AN
OVERVIEW
OF
N-HETEROCYCLIC
CARBENE
..............................................................
11
3.3
BIOLOGICAL
MODELLING
OF
BRESLOW
INTERMEDIATE
......................................................
12
3.4
CYANIDE-CATALYZED
BENZOIN
CONDENSATION
..........................................................
13
3.5
NHC-CATALYZED
BENZOIN
CONDENSATION
................................................................
14
3.5.1
MECHANISTIC
STUDIES
ON
NHC-CATALYZED
BENZOIN
CONDENSATION
...................
16
3.6
NHC-CATALYZED
UMPOLUNG
OF
A,P-SUBSTITUTED
ENALS
...........................................
17
3.6.1
HOMOENOLATES
.................................................................................................
1
3.6.2
NHC-CATALYZED
GENERATION
OF
AZOLIUM
ENOLATE
.............................................
22
3.7
EXPLOITATION
OF
ELECTRON
DEFICIENT
NHC
PRECURSORS
BEARING
CEFS
GROUPS
IN
ORGANOCATALYSIS
............................................................................................................
24
3.8
AN
ACIDITY
DETERMINATION
OF
N-HETEROCYCLIC
CARBENE
PRECURSORS
......................28
4.
CONCEPT
...................................................................................................................30
4.1
BRESLOW
INTERMEDIATES
FROM
AROMATIC
N-HETEROCYCLIC
CARBENES
(BENZIMIDAZOLIN-
2-YLIDENES)
...................................................................................................................
30
4.2
APPLICATIONS
OF
BIS-DIPP/MES-BENZIMIDAZOLIUM
SALTS
IN
ORGANOCATALYSIS
.......
31
4.3
SYNTHESIS
OF
NOVEL
ELECTRON
DEFICIENT
TRIAZOLIUM
NHC
PRECURSORS
BEARING
CEFS
GROUPS
...........................................................................................................................33
5.
RESULTS
.....................................................................................................................
35
5.1
SYNTHESIS
OF
BENZIMIDAZOLIUM
SALTS
20-26,
2-CI
AND
3-CI
..............................35
5.1.1
SYNTHESIS
OF ^-SUBSTITUTED
BENZIMIDAZOLE
DERIVATIVES
125A-C
................35
5.1.2
SYNTHESIS
OF
A/-METHYL
SUBSTITUTED
BENZIMIDAZOLIUM
SALTS
24-26
...............
35
5.1.3
SYNTHESIS
OF
DISUBSTITUTED
BENZIMIDAZOLIUM
SALTS
20-23
............................36
5.1.4
SYNTHESIS
OF
THE
STERICALLY
HINDERED
BENZIMIDAZOLIUM
SALTS
BEARING
MES
OR
DIPP
GROUPS
2CI
AND
3CI
.......................................................................................37
5.2.
GENERATION
OF
BRESLOW
INTERMEDIATES
FROM
BENZIMIDAZOLIN-2-YLIDENES
..........39
5.2.1
SYNTHESIS
OF
FREE
BENZIMIDAZOLIN-2-YLIDENES
2
AND
3
..................................39
5.2.2
SYNTHESIS
OF
BRESLOW
INTERMEDIATES,
DIAMINO
ENOLS
6-10
...........................
40
5.3
NHC
CATALYZED
FORMATION
OF
Y-BUTYROLACTONE
.......................................................
43
5.4
NHC
CATALYZED
DIASTEREOSELECTIVE
SYNTHESIS
OF
Y-LACTAMS
WITH
BIS-MES/DIPP
SUBSTITUTED
BENZIMIDAZOLIUM
SALTS
............................................................................
46
5.5
SYNTHESIS
OF
NEW
ELECTRON
DEFICIENT
NHC
PRECURSORS
.........................................53
5.5.1
SYNTHESIS
OF
BENZAMIDE
DERIVATIVES
40A-C
.................................................53
5.5.2
SYNTHESIS
OF
IMIDOYL
CHLORIDE
DERIVATIVES
41A-C
...........................................
53
5.5.3
SYNTHESIS
OF
BENZOHYDRAZONAMIDE
DERIVATIVES
43A-C
................................54
5.5.4
SYNTHESIS
OF
TRIAZOLIUM
CHLORIDE
SALT
DERIVATIVES
28A-C-CI
........................55
5.5.5
SYNTHESIS
OF
TRIAZOLIUM
TETRAPHENYL
BORATE
SALTS
28B-BPH4
........................
56
6.
DISCUSSION
...............................................................................................................59
6.1
TYPICAL
CHARACTERISTIC
13
C
SHIFT
OF
C=C
DOUBLE
BOND
OF
BRESLOW
INTERMEDIATES
59
6.2
MECHANISTIC
CONSIDERATION
ON
THE
FORMATION
OF
Y-BUTYROLACTONES
FROM
A-METHYL
SUBSTITUTED
ENAL
............................................................................................................
61
6.3
SYNTHESIS
OF
Y-LACTAMS
CATALYZED
BY
BIS-MES/DIPP
SUBSTITUTED
BENZIMIDA
ZOLIUM
SALTS
...................................................................................................................62
6.3.1
REACTION
PROGRESS
USING
NMR-STUDIES
ON
THE
EFFECTS
OF
DIPP/MES
GROUPS
OF
BENZIMIDAZOLIUM
SALTS
TO
DIASTEREOSELECTIVITY
OF
LACTAMS
.................................
62
6.3.2
REACTION
OBSERVATION
FOR
THE
POSSIBLE
ISOMERIZATION
OF LACTAMS
................
63
6.4
SYNTHESIS
OF
NEW
ELECTRON
DEFICIENT
NHC
PRECURSORS
..........................................65
6.4.1
EFFICIENT
SYNTHETIC
APPROACH
FOR
TRIAZOLIUM
PRECURSORS
...................................
65
6.4.2
THE
COMMON
BY-PRODUCT
OBSERVED
IN
THE
RING
CLOSURE
REACTION
OF
TRIAZOLIUM
SALTS
...........................................................................................................................
66
7.
OUTLOOK
.....................................................................................................................68
8.
EXPERIMENTAL
SECTION
.............................................................................................70
8.1
GENERAL
EXPERIMENTAL
CONDITIONS
.......................................................................70
II
8.2
GENERAL
PROCEDURE
(GP1)
FOR
THE
SYNTHESIS
OF
/V-SUBSTITUTED
BENZIMIDAZOLE
DERIVATIVES
73
8.2.1
SYNTHESIS
OF
1-PHENYL-1H-BENZO[D]IMIDAZOLE
(125A)
73
8.2.2
SYNTHESIS
OF
1-(2-NITROPHENYL)-1H-BENZO[D]IMIDAZOLE
(125B)
74
8.2.3
SYNTHESIS
OF
1-(3-NITROPHENYL)-1H-BENZO[D]IMIDAZOLE
(125C)
75
8.3
GENERAL
PROCEDURE
(GP2)
FOR
METHYL
SUBSTITUTED
BENZIMIDAZOLIUM
SALTS
76
8.3.1
SYNTHESIS
OF
3-METHYL-1-PHENYL-1/7-BENZO[D]IMIDAZOL-3-IUM
IODIDE
(24)...
77
8.3.2
SYNTHESIS
OF
3-METHYL-1-(2-NITROPHENYL)-1H-BENZO[D]IMIDAZOL-3-IUM
IODIDE
(25)
77
8.3.3
SYNTHESIS
OF
3-METHYL-1-(3-NITROPHENYL)-1H-BENZO[D]IMIDAZOL-3-IUM
IODIDE
(26)
78
8.4
SYNTHESIS
OF
DI
SUBSTITUTED
ME/ET//PR/PH
BENZIMIDAZOLIUM
SALTS
79
8.4.1
SYNTHESIS
OF
1,3-DIMETHYL-1/-/-BENZO[D]IMIDAZOL-3-IUM
IODIDE
(20)
79
8.4.2
SYNTHESIS
OF
1,3-DIETHYL-1H-BENZO[D]IMIDAZOL-3-IUM
IODIDE
(21)
80
8.4.3
SYNTHESIS
OF
1,3-DIISOPROPYL-1H-BENZO[D]IMIDAZOL-3-IUM
BROMIDE
(22)
82
8.4.4
SYNTHESIS
OF
1
,3-DIMETHYL-1
H-BENZO[D]IMIDAZOL-3-IUM
TETRAFLUORBORATE
(23)
83
8.5
SYNTHESIS
OF
A/,/V-BIS(2,4,6-TRIMETHYLPHENYL)BENZENE-1,2-DIAMINE
(128A)
......84
8.6
SYNTHESIS
OF
/V,A/-BIS(2,4,6-TRIMETHYLPHENYL)BENZENE-1,2-DIAMINE
(128B)
......86
8.7
SYNTHESIS
OF
1,3-BIS(2,4,6-TRIMETHYLPHENYL)-1H-BENZO[D]IMIDAZOLE-3-IUM
CHLORIDE
(2-
CL)
88
8.8
SYNTHESIS
OF
1,3-BIS[2,6-DIISOPROPYLPHENYL]-1/-/-BENZO[D]IMID-AZOLE-3-IUM
CHLORIDE
(3-CI)
90
8.9
SYNTHESIS
OF
4-METHOXY-/V-(4-METHYLBENZYLIDENE)BENZENESULFONAMIDE
(33)..
92
8.10
GENERAL
PROCEDURE
(GP3)
FOR
THE
SYNTHESIS
OF
A,|3-ENALS
93
8.10.1
SYNTHESIS
OF
(E)-4-(3-OXOPROP-1-EN-YL)BENZONITRILE
(32F)
94
8.10.2
SYNTHESIS
OF
(E)-3-(4-(TRIFLUOROMETHYL)PHENYL)ACRYLALDEHYDE
(32G)
95
8.10.3
SYNTHESIS
OF
(E)-3-(3-(TRIFLUOROMETHYL)PHENYL)ACRYLALDEHYDE
(32H)
96
8.11
GENERAL
PROCEDURE
(GP4)
OF
THE
SYNTHESIS
OF
FREE
BENZIMIDAZOLIN-2-YLIDENES
97
8.11.1
SYNTHESIS
OF
1
,3-DIHYDRO-1,3-BIS(2,4,6-TRIMETHYLPHENYL)-2/7-BENZIMIDAZOL-
2-YLIDENE
(2-CI)
97
8.11.2
SYNTHESIS
OF
1
,3-BIS[2,6-BIS(1-METHYLETHYL)PHENYL]-1
,
3-DIHYDRO-2
H-
BENZIMIDAZOL-2-YLIDENE
(3-CI)
100
III
8.12
GENERAL
PROCEDURE
(GP5)
FOR
GENERATION
OF
BRESLOW
INTERMEDIATES
FROM
BENZIMIDAZOLIN-2-YLIDENES
AND
LMIDAZOLIDIN-2-YLIDENES
103
8.12.1
SYNTHESIS
OF
4-[[1,3-BIS[2,6-BIS(1-METHYLETHYL)PHENYL]-1,3-DIHYDRO-2H-
BENZIMIDAZOL-2-YLIDENE]HYDROXYMETHYL]BENZONITRILE
(7)
103
8.12.2
SYNTHESIS
OF
A-[1,3-BIS[2,6-BIS(1-METHYLETHYL)PHENYL]-1,3-DIHYDRO-2/-/-
BENZIMIDAZOL-2
YLIDENE]-4-BROMOBENZENEMETHANOL
(8)
105
8.12.3
SYNTHESIS
OF
A-[1,3-BIS[2,6-BIS(1-METHYLETHYL)PHENYL]-1
,
3-DIHYDRO-2
H-
BENZIMIDAZOL-2-YLIDENE]-2,4-BIS(TRIFLUOROMETHYL)BENZENEMETHANOL
(9)
106
8.12.4
SYNTHESIS
OF
4-[[1,3-DIHYDRO-1,3-BIS(2,4,6-TRIMETHYLPHENYL)-2H-
BENZIMIDAZOL-2-YLIDENE]HYDROXYMETHYL]BENZONITRILE
(10)
109
8.13
SYNTHESIS
OF
BENZAMIDE
DERIVATIVES
111
8.13.1
SYNTHESIS
OF
/V-PHENYLBENZAMIDE
(40A)
111
8.13.2
SYNTHESIS
OF
A/-(2,6-DIISOPROPYLPHENYL)BENZAMIDE
(40B)
112
8.13.3
SYNTHESIS
OF
A/-(3,5-BIS(TRIFLUOROMETHYL)PHENYL)BENZAMIDE
(40C)
113
8.14
SYNTHESIS
OF
IMIDOYL
CHLORIDE
DERIVATIVES
115
8.14.1
SYNTHESIS
OF
A/-PHENYLBENZIMIDOYL
CHLORIDE
(41A)
115
8.14.2
SYNTHESIS
OF
A/-(2,6-DIISOPROPYLPHENYL)BENZIMIDOYL
CHLORIDE
(41B)
116
8.14.3
SYNTHESIS
OF
A/-(3,5-BIS(TRIFLUOROMETHYL)PHENYL)BENZIMIDOYL
CHLORIDE
(41C)
117
8.15
SYNTHESIS
OF
BENZOHYDRAZONAMIDE
DERIVATIVES
118
8.15.1
SYNTHESIS
OF
A/-(PERFLUOROPHENYL)-A/-PHENYLBENZOHYDRAZONAMIDE
(43A)
118
8.15.2
SYNTHESIS
OF
A/-(2,6-DIISOPROPYLPHENYL)-A/-(PERFLUOROPHENYL)BENZO-
HYDRAZONAMIDE
(43B)
120
8.15.3
SYNTHESIS
OF
A/-(3,5-BIS(TRIFLUOROMETHYL)PHENYL)-A/-(PERFLUOROPHENYL)-
BENZOHYDRAZONAMIDE
(43C)
121
8.16
SYNTHESIS
OF
TRIAZOLIUM
CHLORIDE
SALTS
DERIVATIVES
123
8.16.1
SYNTHESIS
OF
1-(PERFLUOROPHENYL)-3,4-DIPHENYL-4H-1,2,4-TRIAZOL-1-IUM
CHLORIDE
(28A-CL)
123
8.16.2
SYNTHESIS
OF
4-(2,6-DIISOPROPYLPHENYL)-1-(PERFLUOROPHENYL)-3-PHENYL-4/-/-
1,2,4-TRIAZOL-1-IUM
CHLORIDE
(28B*CI)
125
8.16.3
SYNTHESIS
OF
4-(3,5-BIS(TRIFLUOROMETHYL)PHENYL)-1
-(PERFLUOROPHENYL)-3-
PHENYL-4H-1,2,4-TRIAZOL-1-IUM
CHLORIDE
(28C*CI)
127
8.17
COUNTERANION
EXCHANGES
130
IV
8.17.1
SYNTHESIS
OF
1-(PERFLUOROPHENYL)-3,4-DIPHENYL-4H-1,2,4-TRIAZOL-1-IUM
TETRAPHENYLBORATE
(28A*BPH4)
130
8.17.2
SYNTHESIS
OF
4-(2,6-DIISOPROPYLPHENYL)-1-(PERFLUOROPHENYL)-3-PHENYL-4H-
1,2,4-TRIAZOL-1-IUM
TETRAPHENYLBORATE
(28BBPH4)
133
8.18
SYNTHESIS
OF
Y-BUTYROLACTONES
137
8.18.1
SYNTHESIS
OF
3-METHYL-4,5-DIPHENYL-5-(TRIFLUOROMETHYL)DIHYDROFURAN-2-ONE
137
8.19
NHC
CATALYZED
DIASTEREOSELECTIVE
SYNTHESIS
OF
Y-LACTAMS
WITH
BIS
MES/DIPP
SUBSTITUTED
BENZIMIDAZOLIUM
SALTS
139
8.19.1
GENERAL
PROCEDURE
(GP6)
FOR
DIASTEREOSELECTIVE
SYNTHESIS
OF
Y-LACTAMS
139
8.19.1.2
SYNTHESIS
OF
1-(4-METHOXYPHENYLSULFONYL)-4-PHENYL-5-P-TOLYL
PYRROLIDIN-
2-ONE
(34A)
140
8.20
SOLVENT
EFFECTS
ON
DIASTEREOSELECTIVITY
OF
THE
DESIRED
PRODUCT
LACTAMS
144
8.21
GENERAL
PROCEDURE
(GP7)
FOR
THE
SYNTHESIS
OF
Y-LACTAMS
(34B
*
I)
145
8.21.1
SYNTHESIS
OF
4-(4-(DIMETHYLAMINO)PHENYL)-1-((4-METHOXYPHENYL)-SULFONYL)-
5-(P-TOLYL)-PYRROLIDIN-2-ONE
(34B)
146
8.21.2
SYNTHESIS
OF
4-(4-METHOXYPHENYL)-1-((4-METHOXYPHENYL)SULFONYL)-5-(P-
TOLYL)PYRROLIDIN-2-ONE
(34C)
148
8.21.3
SYNTHESIS
OF
4-(4-CHLOROPHENYL)-1
-((4-METHOXYPHENYL)SULFONYL)-5-(P-
TOLYL)PYRROLIDIN-2-ONE
(34D)
150
8.21.4
SYNTHESIS
OF
4-(4-BROMOPHENYL)-1-((4-METHOXYPHENYL)SULFONYL)-5-(P-
TOLYL)PYRROLIDIN-2-ONE
(34E)
155
8.21.5
SYNTHESIS
OF
4-(4-METHOXYPHENYL)-1-((4-METHOXYPHENYL)SULFONYL)-5-(P-
TOLYL)PYRROLIDIN-2-ONE
(34F)
157
8.21.6
SYNTHESIS
OF
1-((4-METHOXYPHENYL)SULFONYL)-5-(P-TOLYL)-4-(4-(TRIFLUORO-
METHYL)PHENYL)-PYRROLIDIN-2-ONE
(34G)
159
8.21.7
SYNTHESIS
OF
1-((4-METHOXYPHENYL)SULFONYL)-5-(P-TOLYL)-4-(3-
(TRIFLUOROMETHYL)-PHENYL)-PYRROLIDIN-2-ONE
(34H)
161
8.21.8
SYNTHESIS
OF
1-((4-METHOXYPHENYL)SULFONYL)-4-(4-NITROPHENYL)-5-(P-
TOLYL)PYRROLIDIN-2-ONE
(34I)
163
8.22
REACTION
OBSERVATION
FOR
THE
POSSIBLE
ISOMERIZATION
OF
4-(4-METHOXY-PHENYL)-
1
-((4-METHOXYPHENYL)-SULFONYL)-5-(P-TOLYL)PYRROLIDIN-2-ONE
(34C)
..........................165
V
9.
REFERENCES
.............................................................................................................
166
10.
APPENDIX
................................................................................................................172
10.1
ABBREVIATIONS
.....................................................................................................
172
10.2
NMR
SPECTRA
.....................................................................................................
174
10.2.1
NMR
SPECTRA
OF
1
,3-DIHYDRO-1,3-BIS(2,4,6-TRIMETHYLPHENYL)-2H-
BENZIMIDAZOL-2-YLIDENE
(2)
.....................................................................................
174
10.2.2
NMR
SPECTRA
OF
1,3-BIS[2,6-BIS(1-METHYLETHYL)PHENYL]-1,3-DIHYDRO-2/-/-
BENZIMIDAZOL-2-YLIDENE
(3)
.....................................................................................
175
10.2.3
NMR
SPECTRA
OF
4-[[1,3-BIS[2,6-BIS(1-METHYLETHYL)PHENYL]-1
J
3-DIHYDRO-2H-
BENZIMIDAZOL-2-YLIDENE]HYDROXYMETHYL]BENZONITRILE
(7)
....................................
176
10.2.4
NMR
SPECTRA
OF
A-[1,3-BIS[2,6-BIS(1-METHYLETHYL)PHENYL]-1,3-DIHYDRO-2H-
BENZIMIDAZOL-2-YLIDENE]-4-BROMOBENZENEMETHANOL
(8)
....................................
179
10.2.5
NMR
SPECTRA
OF
A-[1,3-BIS[2,6-BIS(
1
-METHYLETHYL
)PHENYL]-1,3-DIHYDRO-2/7-
BENZIMIDAZOL-2-YLIDENE]-2,4-BIS(TRIFLUOROMETHYL)BENZENEMETHANOL
(9)
.............
180
10.2.6
NMR
SPECTRA
OF
4-[[1,3-DIHYDRO-1,3-BIS(2
A6-TRIMETHYLPHENYL)-2H-
BENZIMIDAZOL-2-YLIDENE]HYDROXYMETHYL]BENZONITRILE
(10)
..................................
182
10.2.7
NMR
SPECTRA
OF
4-(4-CHLOROPHENYL)-1-((4-METHOXYPHENYL)SULFONYL)-5-(P-
TOLYL)PYRROLIDIN-2-ONE
(C/S-34D)
..............................................................................
185
10.2.8
NMR
SPECTRA
OF
1-(PERFLUOROPHENYL)-3,4-DIPHENYL-4/-/-1,2,4-TRIAZOL-1-IUM
CHLORIDE
(28A*CI)
....................................................................................................
188
10.2.9
NMR
SPECTRA
OF
4-(2,6-DIISOPROPYLPHENYL)-1-(PERFLUOROPHENYL)-3-PHENYL-
4H-1,2,4-TRIAZOL-1-IUM
CHLORIDE
(28BCI)
...............................................................
189
10.2.10
NMR
SPECTRA
OF
4-(3,5-BIS(TRIFLUOROMETHYL)PHENYL)-1-(PERFLUOROPHENYL)-3-
PHENYL-4H-1,2,4-TRIAZOL-1-IUM
CHLORIDE
(28C*CI)
...................................................
190
10.3
ABSTRACT
..............................................................................................................
191
10.4
KURZZUSAMMENFASSUNG
....................................................................................
192
10.5
ERKLARUNG
............................................................................................................
193
10.6
LEBENSLAUF
..........................................................................................................
194
VI
|
| adam_txt |
TABLE
OF
CONTENTS
1.
SUMMARY
.
1
1.1
CHARACTERIZATION
AND
REACTIVITY
OF
FIRST
BRESLOW
INTERMEDIATES
FROM
AROMATIC
N-
HETEROCYCLIC
CARBENES
.
1
1.2
APPLICATIONS
OF
NHC
CATALYSIS
FOR
THE
FORMATION
OF
Y-BUTYROLACTONE
FROM
ENAL
.
3
1.3
APPLICATIONS
OF
NHC
CATALYSIS
FOR
THE
FORMATION
OF
Y-LACTAMS
FROM
ENALS
.
5
1.4
SYNTHESIS
AND
CHARACTERISATION
OF
NOVEL
ELECTRON
DEFICIENT
TRIAZOLIUM
PRECURSORS
BEARING
CEFS
GROUPS
.
7
2.
INTRODUCTION
.
9
3.
BACKGROUND
.
10
3.1
AN
OVERVIEW
OF
CARBENE
.
10
3.2
AN
OVERVIEW
OF
N-HETEROCYCLIC
CARBENE
.
11
3.3
BIOLOGICAL
MODELLING
OF
BRESLOW
INTERMEDIATE
.
12
3.4
CYANIDE-CATALYZED
BENZOIN
CONDENSATION
.
13
3.5
NHC-CATALYZED
BENZOIN
CONDENSATION
.
14
3.5.1
MECHANISTIC
STUDIES
ON
NHC-CATALYZED
BENZOIN
CONDENSATION
.
16
3.6
NHC-CATALYZED
UMPOLUNG
OF
A,P-SUBSTITUTED
ENALS
.
17
3.6.1
HOMOENOLATES
.
1
3.6.2
NHC-CATALYZED
GENERATION
OF
AZOLIUM
ENOLATE
.
22
3.7
EXPLOITATION
OF
ELECTRON
DEFICIENT
NHC
PRECURSORS
BEARING
CEFS
GROUPS
IN
ORGANOCATALYSIS
.
24
3.8
AN
ACIDITY
DETERMINATION
OF
N-HETEROCYCLIC
CARBENE
PRECURSORS
.28
4.
CONCEPT
.30
4.1
BRESLOW
INTERMEDIATES
FROM
AROMATIC
N-HETEROCYCLIC
CARBENES
(BENZIMIDAZOLIN-
2-YLIDENES)
.
30
4.2
APPLICATIONS
OF
BIS-DIPP/MES-BENZIMIDAZOLIUM
SALTS
IN
ORGANOCATALYSIS
.
31
4.3
SYNTHESIS
OF
NOVEL
ELECTRON
DEFICIENT
TRIAZOLIUM
NHC
PRECURSORS
BEARING
CEFS
GROUPS
.33
5.
RESULTS
.
35
5.1
SYNTHESIS
OF
BENZIMIDAZOLIUM
SALTS
20-26,
2-CI
AND
3-CI
.35
5.1.1
SYNTHESIS
OF ^-SUBSTITUTED
BENZIMIDAZOLE
DERIVATIVES
125A-C
.35
5.1.2
SYNTHESIS
OF
A/-METHYL
SUBSTITUTED
BENZIMIDAZOLIUM
SALTS
24-26
.
35
5.1.3
SYNTHESIS
OF
DISUBSTITUTED
BENZIMIDAZOLIUM
SALTS
20-23
.36
5.1.4
SYNTHESIS
OF
THE
STERICALLY
HINDERED
BENZIMIDAZOLIUM
SALTS
BEARING
MES
OR
DIPP
GROUPS
2CI
AND
3CI
.37
5.2.
GENERATION
OF
BRESLOW
INTERMEDIATES
FROM
BENZIMIDAZOLIN-2-YLIDENES
.39
5.2.1
SYNTHESIS
OF
FREE
BENZIMIDAZOLIN-2-YLIDENES
2
AND
3
.39
5.2.2
SYNTHESIS
OF
BRESLOW
INTERMEDIATES,
DIAMINO
ENOLS
6-10
.
40
5.3
NHC
CATALYZED
FORMATION
OF
Y-BUTYROLACTONE
.
43
5.4
NHC
CATALYZED
DIASTEREOSELECTIVE
SYNTHESIS
OF
Y-LACTAMS
WITH
BIS-MES/DIPP
SUBSTITUTED
BENZIMIDAZOLIUM
SALTS
.
46
5.5
SYNTHESIS
OF
NEW
ELECTRON
DEFICIENT
NHC
PRECURSORS
.53
5.5.1
SYNTHESIS
OF
BENZAMIDE
DERIVATIVES
40A-C
.53
5.5.2
SYNTHESIS
OF
IMIDOYL
CHLORIDE
DERIVATIVES
41A-C
.
53
5.5.3
SYNTHESIS
OF
BENZOHYDRAZONAMIDE
DERIVATIVES
43A-C
.54
5.5.4
SYNTHESIS
OF
TRIAZOLIUM
CHLORIDE
SALT
DERIVATIVES
28A-C-CI
.55
5.5.5
SYNTHESIS
OF
TRIAZOLIUM
TETRAPHENYL
BORATE
SALTS
28B-BPH4
.
56
6.
DISCUSSION
.59
6.1
TYPICAL
CHARACTERISTIC
13
C
SHIFT
OF
C=C
DOUBLE
BOND
OF
BRESLOW
INTERMEDIATES
59
6.2
MECHANISTIC
CONSIDERATION
ON
THE
FORMATION
OF
Y-BUTYROLACTONES
FROM
A-METHYL
SUBSTITUTED
ENAL
.
61
6.3
SYNTHESIS
OF
Y-LACTAMS
CATALYZED
BY
BIS-MES/DIPP
SUBSTITUTED
BENZIMIDA
ZOLIUM
SALTS
.62
6.3.1
REACTION
PROGRESS
USING
NMR-STUDIES
ON
THE
EFFECTS
OF
DIPP/MES
GROUPS
OF
BENZIMIDAZOLIUM
SALTS
TO
DIASTEREOSELECTIVITY
OF
LACTAMS
.
62
6.3.2
REACTION
OBSERVATION
FOR
THE
POSSIBLE
ISOMERIZATION
OF LACTAMS
.
63
6.4
SYNTHESIS
OF
NEW
ELECTRON
DEFICIENT
NHC
PRECURSORS
.65
6.4.1
EFFICIENT
SYNTHETIC
APPROACH
FOR
TRIAZOLIUM
PRECURSORS
.
65
6.4.2
THE
COMMON
BY-PRODUCT
OBSERVED
IN
THE
RING
CLOSURE
REACTION
OF
TRIAZOLIUM
SALTS
.
66
7.
OUTLOOK
.68
8.
EXPERIMENTAL
SECTION
.70
8.1
GENERAL
EXPERIMENTAL
CONDITIONS
.70
II
8.2
GENERAL
PROCEDURE
(GP1)
FOR
THE
SYNTHESIS
OF
/V-SUBSTITUTED
BENZIMIDAZOLE
DERIVATIVES
73
8.2.1
SYNTHESIS
OF
1-PHENYL-1H-BENZO[D]IMIDAZOLE
(125A)
73
8.2.2
SYNTHESIS
OF
1-(2-NITROPHENYL)-1H-BENZO[D]IMIDAZOLE
(125B)
74
8.2.3
SYNTHESIS
OF
1-(3-NITROPHENYL)-1H-BENZO[D]IMIDAZOLE
(125C)
75
8.3
GENERAL
PROCEDURE
(GP2)
FOR
METHYL
SUBSTITUTED
BENZIMIDAZOLIUM
SALTS
76
8.3.1
SYNTHESIS
OF
3-METHYL-1-PHENYL-1/7-BENZO[D]IMIDAZOL-3-IUM
IODIDE
(24).
77
8.3.2
SYNTHESIS
OF
3-METHYL-1-(2-NITROPHENYL)-1H-BENZO[D]IMIDAZOL-3-IUM
IODIDE
(25)
77
8.3.3
SYNTHESIS
OF
3-METHYL-1-(3-NITROPHENYL)-1H-BENZO[D]IMIDAZOL-3-IUM
IODIDE
(26)
78
8.4
SYNTHESIS
OF
DI
SUBSTITUTED
ME/ET//PR/PH
BENZIMIDAZOLIUM
SALTS
79
8.4.1
SYNTHESIS
OF
1,3-DIMETHYL-1/-/-BENZO[D]IMIDAZOL-3-IUM
IODIDE
(20)
79
8.4.2
SYNTHESIS
OF
1,3-DIETHYL-1H-BENZO[D]IMIDAZOL-3-IUM
IODIDE
(21)
80
8.4.3
SYNTHESIS
OF
1,3-DIISOPROPYL-1H-BENZO[D]IMIDAZOL-3-IUM
BROMIDE
(22)
82
8.4.4
SYNTHESIS
OF
1
,3-DIMETHYL-1
H-BENZO[D]IMIDAZOL-3-IUM
TETRAFLUORBORATE
(23)
83
8.5
SYNTHESIS
OF
A/,/V-BIS(2,4,6-TRIMETHYLPHENYL)BENZENE-1,2-DIAMINE
(128A)
.84
8.6
SYNTHESIS
OF
/V,A/-BIS(2,4,6-TRIMETHYLPHENYL)BENZENE-1,2-DIAMINE
(128B)
.86
8.7
SYNTHESIS
OF
1,3-BIS(2,4,6-TRIMETHYLPHENYL)-1H-BENZO[D]IMIDAZOLE-3-IUM
CHLORIDE
(2-
CL)
88
8.8
SYNTHESIS
OF
1,3-BIS[2,6-DIISOPROPYLPHENYL]-1/-/-BENZO[D]IMID-AZOLE-3-IUM
CHLORIDE
(3-CI)
90
8.9
SYNTHESIS
OF
4-METHOXY-/V-(4-METHYLBENZYLIDENE)BENZENESULFONAMIDE
(33).
92
8.10
GENERAL
PROCEDURE
(GP3)
FOR
THE
SYNTHESIS
OF
A,|3-ENALS
93
8.10.1
SYNTHESIS
OF
(E)-4-(3-OXOPROP-1-EN-YL)BENZONITRILE
(32F)
94
8.10.2
SYNTHESIS
OF
(E)-3-(4-(TRIFLUOROMETHYL)PHENYL)ACRYLALDEHYDE
(32G)
95
8.10.3
SYNTHESIS
OF
(E)-3-(3-(TRIFLUOROMETHYL)PHENYL)ACRYLALDEHYDE
(32H)
96
8.11
GENERAL
PROCEDURE
(GP4)
OF
THE
SYNTHESIS
OF
FREE
BENZIMIDAZOLIN-2-YLIDENES
97
8.11.1
SYNTHESIS
OF
1
,3-DIHYDRO-1,3-BIS(2,4,6-TRIMETHYLPHENYL)-2/7-BENZIMIDAZOL-
2-YLIDENE
(2-CI)
97
8.11.2
SYNTHESIS
OF
1
,3-BIS[2,6-BIS(1-METHYLETHYL)PHENYL]-1
,
3-DIHYDRO-2
H-
BENZIMIDAZOL-2-YLIDENE
(3-CI)
100
III
8.12
GENERAL
PROCEDURE
(GP5)
FOR
GENERATION
OF
BRESLOW
INTERMEDIATES
FROM
BENZIMIDAZOLIN-2-YLIDENES
AND
LMIDAZOLIDIN-2-YLIDENES
103
8.12.1
SYNTHESIS
OF
4-[[1,3-BIS[2,6-BIS(1-METHYLETHYL)PHENYL]-1,3-DIHYDRO-2H-
BENZIMIDAZOL-2-YLIDENE]HYDROXYMETHYL]BENZONITRILE
(7)
103
8.12.2
SYNTHESIS
OF
A-[1,3-BIS[2,6-BIS(1-METHYLETHYL)PHENYL]-1,3-DIHYDRO-2/-/-
BENZIMIDAZOL-2
YLIDENE]-4-BROMOBENZENEMETHANOL
(8)
105
8.12.3
SYNTHESIS
OF
A-[1,3-BIS[2,6-BIS(1-METHYLETHYL)PHENYL]-1
,
3-DIHYDRO-2
H-
BENZIMIDAZOL-2-YLIDENE]-2,4-BIS(TRIFLUOROMETHYL)BENZENEMETHANOL
(9)
106
8.12.4
SYNTHESIS
OF
4-[[1,3-DIHYDRO-1,3-BIS(2,4,6-TRIMETHYLPHENYL)-2H-
BENZIMIDAZOL-2-YLIDENE]HYDROXYMETHYL]BENZONITRILE
(10)
109
8.13
SYNTHESIS
OF
BENZAMIDE
DERIVATIVES
111
8.13.1
SYNTHESIS
OF
/V-PHENYLBENZAMIDE
(40A)
111
8.13.2
SYNTHESIS
OF
A/-(2,6-DIISOPROPYLPHENYL)BENZAMIDE
(40B)
112
8.13.3
SYNTHESIS
OF
A/-(3,5-BIS(TRIFLUOROMETHYL)PHENYL)BENZAMIDE
(40C)
113
8.14
SYNTHESIS
OF
IMIDOYL
CHLORIDE
DERIVATIVES
115
8.14.1
SYNTHESIS
OF
A/-PHENYLBENZIMIDOYL
CHLORIDE
(41A)
115
8.14.2
SYNTHESIS
OF
A/-(2,6-DIISOPROPYLPHENYL)BENZIMIDOYL
CHLORIDE
(41B)
116
8.14.3
SYNTHESIS
OF
A/-(3,5-BIS(TRIFLUOROMETHYL)PHENYL)BENZIMIDOYL
CHLORIDE
(41C)
117
8.15
SYNTHESIS
OF
BENZOHYDRAZONAMIDE
DERIVATIVES
118
8.15.1
SYNTHESIS
OF
A/-(PERFLUOROPHENYL)-A/-PHENYLBENZOHYDRAZONAMIDE
(43A)
118
8.15.2
SYNTHESIS
OF
A/-(2,6-DIISOPROPYLPHENYL)-A/-(PERFLUOROPHENYL)BENZO-
HYDRAZONAMIDE
(43B)
120
8.15.3
SYNTHESIS
OF
A/-(3,5-BIS(TRIFLUOROMETHYL)PHENYL)-A/-(PERFLUOROPHENYL)-
BENZOHYDRAZONAMIDE
(43C)
121
8.16
SYNTHESIS
OF
TRIAZOLIUM
CHLORIDE
SALTS
DERIVATIVES
123
8.16.1
SYNTHESIS
OF
1-(PERFLUOROPHENYL)-3,4-DIPHENYL-4H-1,2,4-TRIAZOL-1-IUM
CHLORIDE
(28A-CL)
123
8.16.2
SYNTHESIS
OF
4-(2,6-DIISOPROPYLPHENYL)-1-(PERFLUOROPHENYL)-3-PHENYL-4/-/-
1,2,4-TRIAZOL-1-IUM
CHLORIDE
(28B*CI)
125
8.16.3
SYNTHESIS
OF
4-(3,5-BIS(TRIFLUOROMETHYL)PHENYL)-1
-(PERFLUOROPHENYL)-3-
PHENYL-4H-1,2,4-TRIAZOL-1-IUM
CHLORIDE
(28C*CI)
127
8.17
COUNTERANION
EXCHANGES
130
IV
8.17.1
SYNTHESIS
OF
1-(PERFLUOROPHENYL)-3,4-DIPHENYL-4H-1,2,4-TRIAZOL-1-IUM
TETRAPHENYLBORATE
(28A*BPH4)
130
8.17.2
SYNTHESIS
OF
4-(2,6-DIISOPROPYLPHENYL)-1-(PERFLUOROPHENYL)-3-PHENYL-4H-
1,2,4-TRIAZOL-1-IUM
TETRAPHENYLBORATE
(28BBPH4)
133
8.18
SYNTHESIS
OF
Y-BUTYROLACTONES
137
8.18.1
SYNTHESIS
OF
3-METHYL-4,5-DIPHENYL-5-(TRIFLUOROMETHYL)DIHYDROFURAN-2-ONE
137
8.19
NHC
CATALYZED
DIASTEREOSELECTIVE
SYNTHESIS
OF
Y-LACTAMS
WITH
BIS
MES/DIPP
SUBSTITUTED
BENZIMIDAZOLIUM
SALTS
139
8.19.1
GENERAL
PROCEDURE
(GP6)
FOR
DIASTEREOSELECTIVE
SYNTHESIS
OF
Y-LACTAMS
139
8.19.1.2
SYNTHESIS
OF
1-(4-METHOXYPHENYLSULFONYL)-4-PHENYL-5-P-TOLYL
PYRROLIDIN-
2-ONE
(34A)
140
8.20
SOLVENT
EFFECTS
ON
DIASTEREOSELECTIVITY
OF
THE
DESIRED
PRODUCT
LACTAMS
144
8.21
GENERAL
PROCEDURE
(GP7)
FOR
THE
SYNTHESIS
OF
Y-LACTAMS
(34B
*
I)
145
8.21.1
SYNTHESIS
OF
4-(4-(DIMETHYLAMINO)PHENYL)-1-((4-METHOXYPHENYL)-SULFONYL)-
5-(P-TOLYL)-PYRROLIDIN-2-ONE
(34B)
146
8.21.2
SYNTHESIS
OF
4-(4-METHOXYPHENYL)-1-((4-METHOXYPHENYL)SULFONYL)-5-(P-
TOLYL)PYRROLIDIN-2-ONE
(34C)
148
8.21.3
SYNTHESIS
OF
4-(4-CHLOROPHENYL)-1
-((4-METHOXYPHENYL)SULFONYL)-5-(P-
TOLYL)PYRROLIDIN-2-ONE
(34D)
150
8.21.4
SYNTHESIS
OF
4-(4-BROMOPHENYL)-1-((4-METHOXYPHENYL)SULFONYL)-5-(P-
TOLYL)PYRROLIDIN-2-ONE
(34E)
155
8.21.5
SYNTHESIS
OF
4-(4-METHOXYPHENYL)-1-((4-METHOXYPHENYL)SULFONYL)-5-(P-
TOLYL)PYRROLIDIN-2-ONE
(34F)
157
8.21.6
SYNTHESIS
OF
1-((4-METHOXYPHENYL)SULFONYL)-5-(P-TOLYL)-4-(4-(TRIFLUORO-
METHYL)PHENYL)-PYRROLIDIN-2-ONE
(34G)
159
8.21.7
SYNTHESIS
OF
1-((4-METHOXYPHENYL)SULFONYL)-5-(P-TOLYL)-4-(3-
(TRIFLUOROMETHYL)-PHENYL)-PYRROLIDIN-2-ONE
(34H)
161
8.21.8
SYNTHESIS
OF
1-((4-METHOXYPHENYL)SULFONYL)-4-(4-NITROPHENYL)-5-(P-
TOLYL)PYRROLIDIN-2-ONE
(34I)
163
8.22
REACTION
OBSERVATION
FOR
THE
POSSIBLE
ISOMERIZATION
OF
4-(4-METHOXY-PHENYL)-
1
-((4-METHOXYPHENYL)-SULFONYL)-5-(P-TOLYL)PYRROLIDIN-2-ONE
(34C)
.165
V
9.
REFERENCES
.
166
10.
APPENDIX
.172
10.1
ABBREVIATIONS
.
172
10.2
NMR
SPECTRA
.
174
10.2.1
NMR
SPECTRA
OF
1
,3-DIHYDRO-1,3-BIS(2,4,6-TRIMETHYLPHENYL)-2H-
BENZIMIDAZOL-2-YLIDENE
(2)
.
174
10.2.2
NMR
SPECTRA
OF
1,3-BIS[2,6-BIS(1-METHYLETHYL)PHENYL]-1,3-DIHYDRO-2/-/-
BENZIMIDAZOL-2-YLIDENE
(3)
.
175
10.2.3
NMR
SPECTRA
OF
4-[[1,3-BIS[2,6-BIS(1-METHYLETHYL)PHENYL]-1
J
3-DIHYDRO-2H-
BENZIMIDAZOL-2-YLIDENE]HYDROXYMETHYL]BENZONITRILE
(7)
.
176
10.2.4
NMR
SPECTRA
OF
A-[1,3-BIS[2,6-BIS(1-METHYLETHYL)PHENYL]-1,3-DIHYDRO-2H-
BENZIMIDAZOL-2-YLIDENE]-4-BROMOBENZENEMETHANOL
(8)
.
179
10.2.5
NMR
SPECTRA
OF
A-[1,3-BIS[2,6-BIS(
1
-METHYLETHYL
)PHENYL]-1,3-DIHYDRO-2/7-
BENZIMIDAZOL-2-YLIDENE]-2,4-BIS(TRIFLUOROMETHYL)BENZENEMETHANOL
(9)
.
180
10.2.6
NMR
SPECTRA
OF
4-[[1,3-DIHYDRO-1,3-BIS(2
A6-TRIMETHYLPHENYL)-2H-
BENZIMIDAZOL-2-YLIDENE]HYDROXYMETHYL]BENZONITRILE
(10)
.
182
10.2.7
NMR
SPECTRA
OF
4-(4-CHLOROPHENYL)-1-((4-METHOXYPHENYL)SULFONYL)-5-(P-
TOLYL)PYRROLIDIN-2-ONE
(C/S-34D)
.
185
10.2.8
NMR
SPECTRA
OF
1-(PERFLUOROPHENYL)-3,4-DIPHENYL-4/-/-1,2,4-TRIAZOL-1-IUM
CHLORIDE
(28A*CI)
.
188
10.2.9
NMR
SPECTRA
OF
4-(2,6-DIISOPROPYLPHENYL)-1-(PERFLUOROPHENYL)-3-PHENYL-
4H-1,2,4-TRIAZOL-1-IUM
CHLORIDE
(28BCI)
.
189
10.2.10
NMR
SPECTRA
OF
4-(3,5-BIS(TRIFLUOROMETHYL)PHENYL)-1-(PERFLUOROPHENYL)-3-
PHENYL-4H-1,2,4-TRIAZOL-1-IUM
CHLORIDE
(28C*CI)
.
190
10.3
ABSTRACT
.
191
10.4
KURZZUSAMMENFASSUNG
.
192
10.5
ERKLARUNG
.
193
10.6
LEBENSLAUF
.
194
VI |
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| author | Sudkaow, Panyapon 1990- |
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| ctrlnum | (OCoLC)1220896773 (DE-599)DNB1217340327 |
| discipline | Chemie / Pharmazie |
| discipline_str_mv | Chemie / Pharmazie |
| format | Thesis Book |
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| illustrated | Illustrated |
| index_date | 2024-07-03T15:35:38Z |
| indexdate | 2024-07-10T08:57:54Z |
| institution | BVB |
| language | English |
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| spelling | Sudkaow, Panyapon 1990- Verfasser (DE-588)1213488761 aut N-heterocyclic carbenes aromatic Breslow intermediates, synthesis of novel electron-deficient NHC catalysts and NHC catalysis vorgelegt von Panyapon Sudkaow Köln 2020 VI, 195 Seiten Illustrationen, Diagramme 21 cm txt rdacontent n rdamedia nc rdacarrier Dissertation Universität Köln 2020 (DE-588)4113937-9 Hochschulschrift gnd-content B:DE-101 application/pdf https://d-nb.info/1217340327/04 Inhaltsverzeichnis DNB Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=032343026&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Sudkaow, Panyapon 1990- N-heterocyclic carbenes aromatic Breslow intermediates, synthesis of novel electron-deficient NHC catalysts and NHC catalysis |
| subject_GND | (DE-588)4113937-9 |
| title | N-heterocyclic carbenes aromatic Breslow intermediates, synthesis of novel electron-deficient NHC catalysts and NHC catalysis |
| title_auth | N-heterocyclic carbenes aromatic Breslow intermediates, synthesis of novel electron-deficient NHC catalysts and NHC catalysis |
| title_exact_search | N-heterocyclic carbenes aromatic Breslow intermediates, synthesis of novel electron-deficient NHC catalysts and NHC catalysis |
| title_exact_search_txtP | N-heterocyclic carbenes aromatic Breslow intermediates, synthesis of novel electron-deficient NHC catalysts and NHC catalysis |
| title_full | N-heterocyclic carbenes aromatic Breslow intermediates, synthesis of novel electron-deficient NHC catalysts and NHC catalysis vorgelegt von Panyapon Sudkaow |
| title_fullStr | N-heterocyclic carbenes aromatic Breslow intermediates, synthesis of novel electron-deficient NHC catalysts and NHC catalysis vorgelegt von Panyapon Sudkaow |
| title_full_unstemmed | N-heterocyclic carbenes aromatic Breslow intermediates, synthesis of novel electron-deficient NHC catalysts and NHC catalysis vorgelegt von Panyapon Sudkaow |
| title_short | N-heterocyclic carbenes |
| title_sort | n heterocyclic carbenes aromatic breslow intermediates synthesis of novel electron deficient nhc catalysts and nhc catalysis |
| title_sub | aromatic Breslow intermediates, synthesis of novel electron-deficient NHC catalysts and NHC catalysis |
| topic_facet | Hochschulschrift |
| url | https://d-nb.info/1217340327/04 http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=032343026&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| work_keys_str_mv | AT sudkaowpanyapon nheterocycliccarbenesaromaticbreslowintermediatessynthesisofnovelelectrondeficientnhccatalystsandnhccatalysis |
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