Rational design of selective anion receptors [Elektronische Ressource] / Denys Meshcheryakov

Denmes

Informations

• Publié par: johannes_gutenberg-universitat_mainz
• Publié le: 01 janvier 2007
• Nombre de lectures: 21
• Langue: English
• Poids de l'ouvrage: 3 Mo

Extrait

Rational design of selective anion
receptors




Dissertation
Zur Erlangung des Grades
„Doktor der Naturwissenschaften“



am Fachbereich für Chemie, Pharmazie und Geowissenschaften
der Johannes-Gutenberg-Universität
in Mainz




Denys Meshcheryakov
geboren in Kiew
Mainz 2006









Contents

1 ANION RECOGNITION: A SURVEY ........................................................................................... 1
1.1 INTRODUCTION ....................................................................................................................... 1
1.2 GENERAL CONSIDERATIONS.................................................................................................... 2
1.3 INTERACTIONS BETWEEN HOST AND THE ANION ..................................................................... 4
1.4 A NEW FAMILY OF UREA-BASED ANION RECEPTORS................................................................ 6
1.5 GENERAL CONSIDERATIONS ON THE SYNTHESIS OF PERSPECTIVE RECEPTORS ...................... 15
1.6 CONCLUSION ........................................................................................................................ 19
2 DEVELOPMENT OF THE GENERAL SYNTHETIC APPROACH........................................ 21
2.1 SYNTHESIS OF DIAMINO UNITS .............................................................................................. 21
2.2 PREPARATION OF BASIC UREAS............................................................................................. 22
2.3 ONE-STEP FORMATION OF CYCLIC OLIGOUREAS FROM DIAMINO UNITS................................. 28
2.4 PROPERTIES OF THE SIMPLEST CYCLES.................................................................................. 31
2.4.1 The eight-membered cyclic “monomer” 41 .................................................................... 32
2.4.2 The cyclic dimer DD 40................................................................................................... 35
2.5 CONCLUSION ........................................................................................................................ 39
3 TRIMERIC CYCLIC OLIGOUREAS: SYNTHESIS AND EVALUATION OF
PROPERTIES.................................................................................................................................. 40
3.1 SYNTHESIS OF TRIMERS ........................................................................................................ 40
3.1.1 Preparation of the XXD trimer 42................................................................................... 41
3.1.2 Preparation of the trimer XXD 43 42
3.1.3 Preparation of the trimer DDD 44.................................................................................. 43
3.1.4 Towards the trimer XXX 17............................................................................................. 44
3.1.5 Preparation of the trimer XXX. ....................................................................................... 46
3.2 X-RAY STRUCTURES ............................................................................................................. 46
3.2.1 Crystal structure of the trimer XXD 42 ........................................................................... 47
3.2.2 ure of the trimer DDD 44 with tetrabutylammonium chloride .................. 49
3.3 COMPLEXATION PROPERTIES OF TRIMERS............................................................................. 51
3.3.1 Trimer XXD 42................................................................................................................ 51
3.3.2 DD 43................................................................................................................ 54
3.3.3 Trimer DDD 44 ............................................................................................................... 55
3.3.4 Trimer XXX 17 56
3.4 CONCLUSION ........................................................................................................................ 58
4 TETRAMERS: SYNTHESIS AND EVALUATION OF COMPLEXATION PROPERTIES. 59
4.1 SYNTHESIS OF TETRAMERS ................................................................................................... 59
4.1.1 “3+1” synthesis: tetramers XXXD, XDXD and XDDD .................................................. 60
4.1.2 “2+2” synthesis: XXDD tetramer...................................................................................62
4.2 X-RAY STRUCTURES..............................................................................................................63
4.2.1 Crystal structure of the tetramer DDDD 39....................................................................63
4.2.2 ures of the tetramer XXXD 5065
4.3 COMPLEXATION PROPERTIES OF TETRAMERS ........................................................................68
4.3.1 Tetramer XXXX 38...........................................................................................................69
4.3.2 Tetramer XXXD 50 ..........................................................................................................70
4.3.3 Tetramer XDXD 5273
4.3.4 Tetramer XXDD 5174
4.3.5 Tetramer XDDD 53 .........................................................................................................76
4.3.6 Tetramer DDDD 3979
4.3.7 Comparison of complexation properties of the tetramers ...............................................81
4.4 CONCLUSIONS.......................................................................................................................86
5 CYCLIC HEXAMERS....................................................................................................................87
5.1 HEXAMER XXXXXX 49 AS A BYPRODUCT IN THE SYNTHESIS OF THE TRIMER XXX............88
5.2 HEXAMER XXDXXD: “2+1+2+1 CYCLIZATION...................................................................90
5.2.1 X-ray structure of the complex of the hexamer XXDXXD with two chloride anions .......90
5.2.2 1H NMR studies of the complexation properties of the hexamer XXDXXD ....................94
5.2.3 Chloride-templated formation of the hexamer XXDXXD ................................................97
5.3 HEXAMER XDDXDD 56.......................................................................................................98
5.3.1 Synthesis of the cyclic hexamer XDDXDD 56 ...............................................................100
5.3.2 X-ray structures of the hexamer XDDXDD ...................................................................101
15.3.3 H NMR studies of the hexamer XDDXDD104
5.4 HEXAMER XDXDXD 55.....................................................................................................106
5.4.1 Synthesis of the cyclic hexamer XDXDXD 55................................................................106
15.4.2 H NMR studies of the hexamer XDXDXD....................................................................107
5.5 TOWARDS HEXAMER DDDDDD 57 ....................................................................................108
5.6 CONCLUSIONS.....................................................................................................................109
6 TOWARDS OLIGOUREAS WITH MORE THAN SIX UNITS. .............................................110
6.1 OLIGOUREA CHAINS BUILT FROM XANTHENE UNITS............................................................110
16.1.1 Synthesis and H NMR spectra of the xanthene-based linear oligomers.......................110
6.1.2 Crystal structure of the linear diamine XXXXX 64........................................................112
6.2 THE LINEAR LONG OLIGOUREA CHAINS ON THE BASIS OF -[XXD]- BLOCKS ........................115
6.3 CONCLUSION.......................................................................................................................118
7 EXPERIMENTAL PART .............................................................................................................119
7.1 DIAMINE 15.........................................................................................................................119
7.2 2,2’-OXYDIANILINE 16 ........................................................................................................119
7.3 TRIMER XXX 17 .................................................................................................................120
7.4 BIS-CARBAMATE 22............................................................................................................ 120
7.5 2,2’-DINITRO DIPHENYL ETHER 23 ...................................................................................... 121
7.6 MONO BOC-PROTECTED X-AMINE 24 ................................................................................ 121
7.7 MONO BOC-ED D-AMINE 25 121
7.8 BOC-PROTECTED DIAMINE XX 26 122
7.9 XX-DIAMINE 27.................................................................................................................. 122
7.10 BOC-PROTECTED DD-DIAMINE 28 .....................................................................................