Synthetic methods in organic and supramolecular chemistry

TITLE PAGE......Page 2
ABSTRACT......Page 4
TABLE OF CONTENTS......Page 6
LIST OF TABLES......Page 7
LIST OF FIGURES......Page 8
LIST OF SCHEMES......Page 9
PREFACE......Page 11
Introduction......Page 12
Figure 1. Competing association events in solution of hosts......Page 16
Figure 2. X-ray structure of Koga’s cyclophane 8 showing inc......Page 17
Table 1.  Binding Data for Hosts 13-17......Page 21
Figure 4. Crystal structure of 17 with xylene.......Page 23
Scheme 1. Cowart’s synthesis......Page 26
Scheme 2. Johnson’s method.......Page 27
Scheme 3. Zawacki’s synthesis.......Page 28
Scheme 4. Jin’s synthesis......Page 29
Scheme 5. Asper’s synthesis.......Page 30
Scheme 6. Retrosynthesis of host 17.......Page 31
Scheme 7. Synthesis of host 17.......Page 32
Scheme 8. Synthesisof host 17 cont’d.......Page 33
Scheme 9. Proposed mechanism for isomerization.......Page 34
Attachment of the Side Arms......Page 35
Table 2. Comparing Binding Data of Host 17 with Host 19.......Page 36
Scheme 12. Synthesis of diphenethylamine (34).......Page 37
Scheme 13. Synthesis of triflate 35.......Page 38
Table 3. Conditions Applied to the Buchwald-Hartwig Reaction......Page 39
Scheme 14. Synthesis of aryl bromide 38.......Page 40
Scheme 15. Synthesis of macrocyclic compounds 42a and 42b.......Page 41
Scheme 16. Hydrolysis of model compound 39.......Page 42
Conclusions......Page 43
Experimental......Page 44
References......Page 60
Introduction......Page 63
Scheme 17. Tethered reactants for intramolecular reactions.......Page 64
Scheme 18. Examples of silicon tethered intramolecular react......Page 65
Scheme 20. Proposed stepwise catalytic alcoholysis of dihydr......Page 66
Scheme 21. Proposed stepwise catalytic alcoholysis of dihydr......Page 67
Table 4. Catalytic Alcoholysis of Diethylsilane, Diphenylsil......Page 69
Scheme 23. Controlled catalytic alcoholysis of diisopropylsi......Page 71
Table 5. Mono-alkoxysilanes 1a-1i.......Page 72
10 % Pd/C Catalyst......Page 73
Table 6.  Alcohol Addition to Ethyl (2S)-2-[(diisopropylsily......Page 74
oxy]propanoate using 10 % Pd/C as the Catalyst.......Page 76
Mn(CO)5Br Catalyst......Page 77
Table 8. Alkenols addition to ethyl (2S)-2-[(diisopropylsily......Page 78
Table 9. Alcohol Addition to Ethyl (2S)-2-[(diisopropylsilyl......Page 79
Intramolecular Radical Translocation Reaction......Page 80
Table 10.  Hydrogen Atom Abstraction versus Radical Quenchin......Page 81
Table 11.  Catalytic Alcoholysis with a Reverse Order Additi......Page 82
Scheme 31. Comparison of the reactivity of 1a versus 1e.......Page 83
Figure 5. General mechanism of silane alcoholysis.......Page 84
Figure 6. Catalytic cycle for Brookhart’s iron catalyst show......Page 85
Figure 7. The metal η2-silane bonding interactions based on......Page 86
Scheme 32. Dimerization of 1e with 10 % Pd/C.......Page 87
Scheme 33. Compounds 1a, 1e and 1f.......Page 88
Scheme 34. Catalytic alcoholysis of 1d with (+)-ethyl lactat......Page 90
Scheme 35. Reaction of 1e with 2-phenylethanol using Mn(CO)5......Page 91
Figure 10. Our first proposed mechanism.......Page 92
Scheme 36. Reaction of benzyl alcohol with 1e in the presenc......Page 95
Similarities Between the 10 % Pd/C and the Mn(CO)5Br Catalys......Page 96
Understanding the Manganese System.......Page 98
Scheme 38.  4-Centered transition state showing the rearrang......Page 99
Figure 11. Proposed mechanism for the formation of symmetric......Page 100
Scheme 39. Deuterium labeled experiment to test for proton t......Page 102
Scheme 40. Evaluation of electronic factors on the extent of......Page 103
Chiral Silanes......Page 104
Table 12.  The Evaluation Silane Alcoholysis of Prochiral Si......Page 105
Conclusion......Page 107
Experimental......Page 109
References......Page 127