Dissertation Synthesis

Dissertation Synthesis-73
The synthesis, properties, and electronic structures of a family of iridium corrole complexes are discussed in detail.These compounds represent the first well-characterized examples of third-row metals being inserted successfully into the small corrole binding pocket; they possess a planar macrocycle, which neither saddles nor ruffles upon bromination, and are bound at the axial positions by either two amine ligands or one phosphine.

Excess of Reagents = Filter Figure 1.2 Purification of compounds bound to the solid support from those in solution by simple filtration.

The solid support describes the insoluble material that is reversibly bound to the starting reactants.

Unfortunately, the quantum yields of phosphorescence are low, 1% or less, and this appears to be due to an exceptionally slow set of radiative rates for the corroles.

An examination of the reactivity of ammine-ligated Ir(III) corroles is also described.

Cylinder to the right shows the main hydrogen bonding in an -helix...64 Figure 3.3 Parallel and antiparallel -sheet hydrogen bonding...65 Figure 3.4 The Fmoc-/Boc-SPPS protecting group strategy...67 Figure 3.5.

Finally I would like to thank all of my committee members for supervising my work with continuous encouragement: Dr. CVERGET PEPTIDE SYTESIS Introduction Secondary Structure Solid-Phase Peptide Synthesis Methods Convergent Peptide Synthesis Convergent Solid-Phase Peptide Synthesis(CSPPS) of Protected Peptide Segments Chemoselective ligation of Unprotected Peptide Fragments Results and Discussion Experimental Peptide Synthesis Cyh Cyh-7 MIC Assays ydroxypalmitoleic Acid Peptide Synthesis Agni[ Glu(-All)(KLAKKLA) 2 heptenoic Acid] Ring Closing Methatesis Peptide Ligation Attempted Peptide Ligation Attempted Peptide Ligation...88 CAPTER 4 CCLUSI AD FUTURE STUDIES Discussion...89 REFERECES VITA...96 v LIST F TABLES Table 1.1 Common protecting groups used in SPPS where side chains are cleaved mild to moderate acidic conditions...5 Table 3.1 Common coupling reagents used in SPPS...69 Table 3.2 Examples of large synthetic peptides and small proteins synthesized by SPPS...70 Table 3.3 Methods for ligating unprotected peptides...75 Table 3.4 Minimum inhibitory concentration of Cyh vi LIST F FIGURES Figure 1.1 Schematic representation of a peptide synthesis...1 Figure 1.2 Purification of compounds bound to the solid support from those in solution by simple filtration...2 Figure 1.3 General scheme for solid-phase peptide synthesis page...4 Figure 1.4 Cleavage of peptide from the linker PAL...7 Figure 1.5 Cleavage of peptide from BAL(Backbone amide linker)...8 Figure 1.6 Cleavage of peptide from trityl resin...9 Figure 1.7 Cleavage of peptide from the Rink linker...10 Figure 1.8 Methoxy substituted benzyl amine linkers...11 Figure 1.9 Peptide cleavage from BDMTA resin...11 Figure 1.10 Cleavage of peptide from BA resin...12 Figure 1.11 Cleavage of peptide from MBA resin...13 Figure 1.12 Peptide cleavage using Alkoxybenzylamine linker...14 Figure 1.13 Peptide cleavage from CA and CE linkers Figure 1.14 Peptide cleavage using the semicarbazide linker...16 Figure ,4'-dimethoxybenzhydryl derived linkers and cleavage conditions...17 Figure 1.16 Peptide cleavage using a dimethoxy diphenyl linker...17 Figure 1.17 Peptide cleavage using MPB linker...18 Figure 1.18 Peptide cleavage using the 2-chlorotrityl linker...19 Figure 1.19 Peptide cleavage from MALDRE linker...19 Figure 1.20 Peptide cleavage from methoxy benzyl amine linker...20 Figure 1.21 Modified Benzhydrylamine linker...21 vii Figure Benzyloxytritylamine linker derivatives...23 Figure 1.23 Peptide cleavage from SCAL linker...24 Figure 1.24 Use of Boc-DSA- -Ala Figure 1.25 Boc-Leu--DSB-ß-Ala--linker...26 Figure 1.26 Benzyl alcohol linkers...26 Figure 1.27 Peptide cleavage from an acetophenone-based linker...27 Figure 1.28 p-alkoxybenzyl linker...28 Figure 1.29 Cleavage of peptide mimetic using MPV linker...28 Figure 1.30 Cleave of peptide using caboxybenzaldehyde resin...29 Figure 1.31 Peptide cleavage using arginyl linker...30 Figure 1.32 Peptide cleavage from oxazolidine linker...30 Figure 1.33 Peptide cleavage from p-aminoanilide linker...31 Figure 1.34 Peptide cleavage from the silyl phenyl linker...32 Figure 1.35 Peptide cleavage using SAL linker...32 Figure 1.36 Peptide cleavage from p-alkoxybenzyl alcohol linker...33 Figure 1.37 Peptide cleavage from p- alkoxybenzyl-oxycarbonylhydrazide linker...34 Figure 1.38 Peptide cleavage from alkyloxycarbonylhydrazide linker...34 Figure 1.39 Peptide cleavage using imidazole trityl resin...35 Figure 2.1 Benzyl amine linker and ferrocenyl amine linker...37 Figure 2.2 rrocenyl carbocation formation by acid cleavage...38 Figure 2.3 rrocene linker on same and different sites of the cyclopentadienyl ligands...38 Figure 2.4 Retrosyntetic analysis of the ferrocene linker...39 viii Figure 2.5 Attempted forward synthetic route...39 Figure 2.6 Failed initial attempts to generate the ferrocenyl amine...40 Figure 2.7 rrocene Friedel-Crafts acylation with methyl adipoyl chloride...41 Figure 2.8 Synthesis of ferrocene linker and coupling to Clear resin...42 Figure 2.9 rrocene 1-carboxylic acid-1`carboxaldehyde synthesis...43 Figure 2.10 rrocene linker amino acid coupling...44 Figure 2.11 rrocene linker synthesis...45 Figure 2.12 Clear- resin magic angle spinning 1 -MR...54 Figure 2.13 rrocene carboxaldehyde resin magic angle spinning 1-MR...55 Figure rrocene linker 1 -MR...56 Figure 3.1 General amino acid structure...63 Figure 3.2 Cylindrical representations of helical secondary structures.

DESIG AD SYTESIS F VEL FERRCEE LIKER Introduction Design of the rrocene Linker Results and Discussion Experimental rrocenyl-4-oxobutanoic Acid Propenyl-4-ferrocenyl-4-oxobutanoate rrocenyl-1-hydrazide butanoic Acid Methyl 4-ferrocenyl-4-oxohexanoate rrocenyl-1 hydrazide hexanoic Acid rrocenyl-1,1'-acid Fluoride Methyl ferrocenecarboxylate Methyl-1'-formyl-1-ferrocene carboxylateferrocene ept-6-enylamine rrocenyl-imine-glycine(ethylester), methoxycarbonyl rrocene-methylglycine-ethyl ester, methoxycarbonyl rrocene-1-carboxylic acid-1`carboxaldehyde rrocene carboxaldehyde Resin rrocenyl heptenoic amine Resin Agni[(KLAKKLA) 2 ] (2.24)using ferrocenyl heptenoic amine Resin rrocene carboxaldehyde-polystyrene Resin Allyl-amino ferrocenyl polystyrene Resin Allyl-amino fmoc-phenylalanine ferrocenyl polystyrene Resin...59 iv Cleavage of (1-allylcarbamoyl-2-phenyl-ethyl)-carbamic acid 9-fluoren-9-ylmethyl ester from allyl-amino ferrocenyl polystyrene Resin...60 CAPTER 3.


Solid-phase reactions can occur on the surface of the solid particles or inside these particles.

There are several types of materials used as solid supports that 2 allow reactions only on the surface, for example, beads made from glass and cellulose fibers2, the reduced surface area in these surface-type solid supports reduces the number of functionalization sites.


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