Synthesis of a polymer with benzoxazine units in the main chain backbone by a trifunctional phenol, a difunctional amine, and paraformaldehyde was achieved. Thermal, mechanical and spectroscopic characterization and the viscosity properties of the synthesized polymer were studied. In the first step of this study, a fast and feasible method for the synthesis of the benzoxazine precursors was developed since some methods mentioned in the literature about the synthesis of the benzoxazine derivatives last long time. The second step was to polymerize the benzoxazine precursors thermally. The curing of benzoxazine precursors was done via ring opening polymerization at 150 oC and a final polymerization was observed at about 250 oC. 1H NMR, 13C NMR and FT-IR spectroscopies revealed the characteristic peaks for the formation of benzoxazine ring. Among them, 13C NMR gave important clue on the formation of the benzoxazine. The thermal characterization of the benzoxazine precursors and the polymers indicated that the ring opening polymerization of these precursors started at around 110 oC and a final polymerization was about at 230 oC. Differential Scanning Calorimetry thermograms of the polybenzoxazine indicated a secondary transition at around 270 oC. An onset decomposition of the benzoxazine oligomers started around 100 oC in Thermal Gravimetric Analysis thermograms performed under N2 atmosphere and two major maximum weight losses were observed at 273 oC and 439 oC. However, polybenzoxazine showed a starting degradation at about 260 oC and the maximum weight loss temperatures were seen at 296 oC and 465 oC. Viscosity variation of the reaction mixture was studied by Ubbelohde Viscometer at 30 oC. Viscosity results indicated that the increase in the intrinsic viscosity of the reaction mixture till 50th minute and followed by a decrease due to possible branching and the intra-crosslinking of the benzoxazine oligomers. Mechanical properties of the polymer films, prepared by compression molding at 180 0C, were investigated. Test results showed that low tensile strength whereas comparatively high elongation.

Cyclitols are cyclic compounds having hydroxyl groups which attached to different carbons on the ring. Cyclitols have attracted a great deal of attention for having diverse biological activities. Cyclic alcohols play an important role in biological processes such as inhibition of glycosidase, cellular recognition, and signal transduction. In addition to this, these compounds are very important molecules due to being capable of using while synthesizing natural products or pharmaceuticals. In this study, development of new methodology for the synthesis of bis-aminoinositol derivatives was aimed. The starting material, cis-diester, was synthesized from the Diels-Alder reaction of furan and maleic anhydride followed by reaction with MeOH. As a second key compound, trans-diester was obtained from the Diels-Alder reaction of furan and fumaryl chloride followed by esterification. The diester functionality in these two compounds was planned to be converted into the hydrazide upon treatment with hydrazine monohydrate. Before this reaction, double bond was protected via stereo selective oxidation reaction with m-CPBA due to preventing retro Diels-Alder reaction. Then, hydrazide functionality was converted into acyl azide through &beta / -nitroso hydrazide intermediate. Subsequent Curtius rearrangement reaction resulted in the formation of the isocyanate which was converted to the corresponding bis-urethane by treatment with MeOH. Attempt to cleave the oxa-bridge in urethane with sulfamic acid provided the unexpected tricyclic product 148. Furthermore, hydrolysis of isocyanate with aqueous HCl formed the diamine 156. However, O-bridge could not be opened with any reagents used for that of urethane derivative as described above. Then,the cis-diol 157 was synthesized to prevent the neighboring group participitation during the epoxide-opening reaction. Further ring-opening reactions are under investigation.

The use of novel hyperbranched aminosilica (HAS) materials created through the ring-opening polymerization of aziridine from mesoporous silica supports was proposed for the adsorption of CO2 from dilute sources. The limits of the adsorptive performance of these adsorbents were investigated via the preparation of sets of materials with a range of aminopolymer loadings on several different silica supports with different pore space characteristics. Relationships were determined between the materials' amine loadings and the CO2 adsorption performance. Adsorbents with substantial remaining pore volume displayed universal adsorption kinetics when normalized by amine loading. However, materials with blocked pores displayed substantially slower adsorption kinetics due to hindered mass transfer. In both humid and dry conditions, the HAS adsorbent was found to have a surprisingly large CO2 capacity in light of the 250-fold reduction in CO2 partial pressure from 10% CO2 (flue gas application) to 400 ppm CO2 (air capture application). Finally, a new series of linear aminosilicas was created through the reaction of existing aminosilicas with N-protected-aziridines. Specifically, reaction of aminosilane-functionalized silicas with N-methylaziridine resulted in the linear growth of methylaminoethyl groups, effectively increasing the amine loading of the adsorbent by a stoichiometric amount of an additional amine per attached silane.

<p>The first part of this thesis describes a synthetic strategythat provides all eight possible isomers of a given vic-aminoalcohol starting from vinylepoxides. The value of a generalroute is evident, as several isomers are needed ininvestigations of structure-activity relationships forpharmacologically active derivatives, and for optimizing theperformance of chiral ligands containing the amino alcoholmoiety.</p><p>Vinylepoxides, obtained in high enantiomeric excess, werering-opened both with inversion and retention ofstereochemistry, delivering two diastereomeric amino alcoholswith high regio- and stereoselectivity. Via ring-closure toaziridines and subsequent regioselective ring-opening withsuitable oxygen nucleophiles, the two remaining amino alcoholswere selectively achieved.</p><p>Within this study, two efficient protocols for theregioselective and stereospecific aminolysis of vinylepoxideshave been presented. Comparedto previous methods, theseprocedures use milder reaction conditions, shorter reactiontimes, generally give higher yields and are applicable to alarger set of substrates. Furthermore, the ring-closure ofvic-amino alcohols to the corresponding N-H vinylaziridines hasbeen investigated. Three routes have been found useful, whichone is preferred depends on substrate and scale.</p><p>In the second part of the thesis, the synthetic strategy isapplied on the synthesis of Sphingosine and its regio- andstereoisomers. Moreover, a rapid way of determining relativeconfiguration of vic-amino alcohols is described, which shouldbe of substantial use when amino alcohols are formed bydiastereoselective reactions.</p><p>amino alcohols, vinylepoxides, vinylaziridines, oxazolines,oxazolidinones, ring-opening, regioselective,diastereoselective, sphingosine, configuration, NMRspectroscopy.</p>

<p>This thesis deals with the design and synthesis of chiralenantiopure nitrogencontaining ligands and the use of theseligands in asymmetric catalysis. A modular synthetic approachto enantiopure nitrogen-containing ligands was developed. Thesynthetic method is based on the ring-opening of activatedchiral aziridines by nitrogen nucleophiles. The aziridines areconveniently prepared from amino alcohols. The structure oftheaziridine and of the nucleophile can be extensively varied andlibraries of ligands are easily prepared. The use of primaryamines affords C₂-symmetric bis(sulfonamides), whereas the use ofammonia affords C₃-symmetric tris(sulfonamides) that can beelaborated into the corresponding tetra-amines.</p><p>The C₂- and C₃-symmetric ligands were used in the asymmetrictitaniummediated addition of diethylzinc to benzaldehyderesulting in modest enantioselection, 76% ee. A thoroughinvestigation of the reaction conditions revealed that theamount of Ti(OiPr)₄has a decisive effect on the reaction rate and thestereochemical outcome of the reaction. The reaction timedecreased from about 90 hours to 15 minutes and theenantioselectivity changed from 26% of the (R)- enantiomer to72% of the (S)-enantiomer when the Ti(OiPr)₄:benzaldehyde ratio was increased from 0.125:1 to1.48:1. Moreover, the titanium-mediated addition of diethylzincto benzaldehyde was studied in the presence of chiraladditives. The bis(sulfonamides) were also used in thecyclopropanation of cinnamyl alcohol. However, only lowenantioselection was observed, 27% ee.</p><p>The C₃-symmetric tetra-amines were reacted to formazaphosphatranes. These weak acids were only partiallydeprotonated by the strong base KOtBu to form the correspondingproazaphosphatranes. The unexpectedly strong basicity of theproazaphosphatranes was believed to be due to steric effects assuggested by DFT calculations. The tetra-amines and thesulfonamides were used for the preparation of metal complexesof Lewis acidic metals such as titanium(IV) andzirconium(IV).</p><p><b>Keywords:</b>asymmetric catalysis, aziridine, benzaldehyde,diethylzinc, enantioselective, ligand, proazaphosphatrane,ring-opening, sulfonamide, symmetry, titanium, zirconium</p>

<p>This thesis deals with the preparation and use of chiralbispyridylamides as ligands in metal-catalyzed asymmetricreactions.</p><p>The compounds were prepared by amide formation usingdifferent coupling reagents. Bispyridylamides havingsubstituents in the 4- or 6- positions of the pyridine ringswere prepared by functional group interconversion of the 4- or6- halopyridine derivatives. These synthetic approaches provedto be useful for various types of chiral backbones. Pseudo C₂-symmetric bispyridylamides were also synthesizedby means of stepwise amide formation.</p><p>The compounds were used as ligands in themicrowave-accelerated Mocatalyzed asymmetric allylic alkylationreaction. Ligands having ð-donating substituents in the4-positions of the pyridine rings gave rise to products withhigher branched to linear ratio. The catalytic reaction, whichproved to be rather general for allylic carbonates with anaromatic substituent, was used as the key step in thepreparation of (R)-baclofen. The Mo-bispyridylamide catalystprecursor was studied by NMR spectroscopy.</p><p>Bispyridylamide complexes of metal alkoxides were alsoevaluated in the asymmetric addition of cyanide to aldehydesand the metal complexes involved were studied by NMRspectroscopy and X-ray crystallography. Chiral diamines wereused as additives to study the ring opening of cyclohexeneoxide with azide, catalyzed by Zr(IV)-bispyridylamidecomplexes.</p><p>Various bispyridylamides were attached to solid supports oforganic or inorganic nature. The solid-supported ligands wereused in Mo-catalyzed asymmetric allylic alkylation reactionsand in the asymmetric addition of cyanide to benzaldehyde.</p><p><b>Keywords:</b>asymmetric catalysis, chiral ligand, pyridine,amide, allylic alkylation, enantioselective, cyanation,ring-opening, chiral Lewis acid.</p>

Αντικείμενο της παρούσας εργασίας ήταν η σύνθεση μιας σειράς τριπολυμερών και ενός πεντασυσταδικού συμπολυμερούς, καθώς και η μελέτη του τρόπου αυτό-οργάνωσής τους σε αραιά υδατικά διαλύματα στα οποία μεταβάλλεται το pH. Τα συμπολυμερή που συντέθηκαν είχαν δομικές μονάδες πολυ(βίνυλο-2-πυριδίνη) P2VP, πολυ(αιθυλενοξείδιο) PEO και πολύ(ε-καπρολακτόνη) PCL. Για την σύνθεση αυτών χρησιμοποιήθηκαν πρόδρομα συμπολυμερή δυο και τριών συστάδων, τα οποία είχαν συντεθεί μέσω ζωντανού ανιονικού πολυμερισμού, και στην συνέχεια με την μέθοδο του πολυμερισμού διάνοιξης δακτυλίου {Ring Opening Polymerization(ROP)} πραγματοποιήθηκε η προσθήκη της ε-CL. Η προσθήκη αυτή πραγματοποιήθηκε με αντίδραση του [Sn(Oct)2] με το ελεύθερο υδροξύλιο του αιθυλενοξειδίου δημιουργώντας έτσι ένα σύμπλοκο που αποτελεί τον εκκινητή, σύμφωνα με τον μηχανισμό εισαγωγής-σύμπλεξης. Ο χαρακτηρισμός των πολυμερών που συντέθηκαν πραγματοποιήθηκε μέσω της Χρωματογραφίας Αποκλεισμού Μεγεθών (SEC) και της Φασματοσκοπίας Πυρηνικού Μαγνητικού Συντονισμού (NMR). Στην συνέχεια προβήκαμε στη μελέτη αραιών υδατικών διαλυμάτων συναρτήσει του pH δυο πολυμερών από αυτά που συνθέσαμε, του πεντασυσταδικού PCL-PEO-P2VP-PEO-PCL και του τριπολυμερούς P2VP-PEO-PCL. Η μελέτη αυτή έγινε μέσω πειραμάτων σκέδασης του φωτός (στατική σκέδαση στις 900 και δυναμική σκέδαση) και μέσω της Ηλεκτρονικής Μικροσκοπίας Σάρωσης (SEM). Τα πολυμερή αυτά αποτελούνται από P2VP της οποίας η συμπεριφορά διαφοροποιείται με τις αλλαγές του pH μετατρέποντάς την σε έναν κατιονικό υδρόφιλο πολυηλεκτρολύτη σε χαμηλές τιμές αυτού, ενώ καθίσταται ηλεκτρικά ουδέτερη καθώς το pH αυξάνει, με αποτέλεσμα να γίνεται υδρόφοβη λόγω της αποπρωτονίωσής της. Η συμπεριφορά αυτή της P2VP σε συνδυασμό με τον υδρόφιλο χαρακτήρα του PEO και τον υδρόφοβο χαρακτήρα της PCL σε όλες τις τιμές του pH, οδήγησε στην δημιουργία πολυμοριακών συσσωματωμάτων σε ορισμένη περιοχή του pH. Μάλιστα το πεντασυσταδικό πολυμερές σχηματίζει σφαιρικά μικκύλια στην συγκεκριμένη περιοχή. Τέλος πρέπει να αναφερθεί ότι η πρωτοτυπία της παρούσας εργασίας εστιάζεται στο γεγονός ότι δεν έχουν μελετηθεί στο παρελθόν συμπολυμερή PCL με PEO και P2VP. Η ιδιότητα των συμπολυμερών που συνθέσαμε να σχηματίζουν πολυμοριακά συσσωματώματα και μικκύλια, ίσως αποβεί πολύ χρήσιμη σε πολλούς τομείς της βιομηχανίας και της βιοϊατρικής. / This project deals with the synthesis of triblock and pentablock copolymers, which were studied in aqueous solutions as a function of pH. The copolymers, which we synthesized, were Poly(2-vinil pyride)-Poly(ethylene oxide)-Poly(ε-caprolactone) (P2VP-PEO-PCL) and Poly(ε-caprolactone)-Poly(ethylene oxide)-Poly(2-vinil pyride)- Poly(ethylene oxide)-Poly(ε-caprolactone) (PCL-PEO-P2VP-PEO-PCL). The triblock and pentablock copolymers were synthesized via the method of Ring Opening Polymerization (ROP), using as initiator the stannous octoate [Sn(Oct)2]. For the triblock copolymers’ synthesis we used the diblock P2VP-PEO, which was synthesized via the method of living anionic polymerization, and for the pentablock copolymer’s synthesis we used the triblock PEO-P2VP-PEO, which was synthesized via the same method. The molecular weights and polydispersities were determined by Size Exclusion Chromatography and their compositions by 1H NMR. The properties of these copolymers were studied in aqueous solutions as a function of pH, by several experimental techniques such as static and dynamic light scattering and Scanning Electron Microscopy (SEM). The copolymers self organized in different nano structured self-assemblies which depend on the solution pH exhibiting therefore a stimuli responsive behavior.

The synthesis and characterization of a series of chiral indium complexes bearing a tridentate NNO ligand are reported. The ligand 2-[[[(dimethylamino)cyclohexyl]amino]methyl]- 4,6-bis(tert-butyl) phenol (H₂NNO) was synthesized via a previously published procedure and bound to indium by both a protonolysis and salt metathesis route. A dimethylated indium complex (NNO)InMe₂ (1) was isolated by reaction of InMe₃ with H₂NNO. A one-pot saltmetathesis route was used to produce a unique mixed-bridge dinuclear indium complex [(NNO)InCl] ₂(μ-OEt)(μ-Cl) (3) from a mixture of indium trichloride, potassium ethoxide and the monopotassiated salt of the ligand, KH(NNO). Direct reaction of KH(NNO) and indium trichloride resulted in the formation of (NNO)InCl₂ (4) which was carried forward to 3 by reaction with sodium ethoxide. The complex 3 is active for the ROP of β-butyrolactone ε-caprolactone and lactide and is the first reported indium-based catalyst for lactide or β-butyrolactone ROP. Kinetic studies of 3 for ROP of LA revealed that catalyst was well-behaved, and that the rate was first order with regard to lactide and catalyst. The enthalpy and entropy of activation for the ROP were experimentally determined. Polymer produced by ROP by 3 has narrow molecular weight distribution and a good correlation is seen between the observed moleular weight and monomer loading. A mechanism was proposed for 3 acting as a catalyst for the ROP of lactide; however further experiments are required to confirm this mechanism. Polymer samples isolated from the ROP of rac-lactide by rac-3 show isotactic enrichment. It is postulated that the chiral catalyst 3 is exerting stereocontrol via an enantiomorphic site control mechanism.

This thesis is an investigation of ruthenium-catalyzed [2+2] cycloaddition reactions of a 3-aza-2-oxabicyclo[2.2.1]hept-5-ene with unsymmetrical alkynes. Yields of up to 90% were obtained though regioselectivity was modest. Select cycloadducts could be separated and used to access a highly functionalized [3.2.0] bicyclic structure through reductive cleavage of the N-O bond. These ring-opened products displayed a chemical exchange phenomenon in 1D carbon NMR and required characterization by 2D NMR techniques. In addition, a haloalkynylation reaction was found to occur when 1-iodo-2-phenylethyne and the 3-aza-2-oxabicyclo[2.2.1]hept-5-ene were submitted to the cycloaddition conditions. An effort was made to optimize the reaction between 1-iodo-2-phenylethyne and norbornadiene in favour of the addition product. / Government of Ontario, NSERC

This report is an investigation of regioselectivity in transition metal catalyzed ring-opening reactions involving unsymmetrical oxabicycles, specifically with a substituent at the C1 position. This report also provides the details of the work conducted towards the preparation of various oxanorbornadienes and their precursors. A large number of reactions have been developed using various transition metal catalysts on oxabicyclic alkenes to form functionalized organic scaffolds. However, most of the literature is limited to symmetrical substrates. Introduction of a substituent at the bridgehead carbon of the bicyclic ring makes the molecule unsymmetrical. The implications of loss of the plane of symmetry in C1 substituted oxabicyclic ring are manifested in interesting ways during various metal catalyzed reactions. The fundamental basis for the current work is to study the consequences of transition metal catalyzed ring opening reactions of unsymmetrical bicyclic alkenes. The reactivity of a wide range of C1 substituted benzoxanorbornadienes and oxanorbornadienes in palladium and nickel-catalyzed ring opening reactions was explored. The palladium catalyzed ring opening reaction of both electron rich and electron deficient C1 substituted benzoxanorbornadienes are optimized. The ring opening reactions with electron withdrawing C1 substituent resulted in formation of substituted naphthalene-1-carboxylic acid methyl ester derivatives in up to 85% yield. Electron donating substituents on the C1 position of benzoxanorbornadiene led to the formation of substituted cis-1,2-dihydronaphthol rings in excellent yields. Palladium catalyzed ring opening reactions were also explored with a wide range of aryl iodides and halobenzenes. The electronic and steric effects of the substituent at the C1 position of oxabicyles were also investigated. The nickel catalyzed ring opening reactions resulted in formation of inseparable regioisomeric mixtures of products. However, it was found that the nickel catalyzed ring opening of 1-methoxycarbonyl-7-oxabenzonorbornadiene occurred regioselectively affording a single product. A scalable procedure for preparation of large quantities of 2-bromofuran was developed. 2-Aryl furans were prepared using Suzuki cross coupling protocols of 2-bromofuran with aryl boronic acids whereas 2-alkyl furans were prepared by iron catalyzed cross coupling reaction of 2-bromofuran with various alkyl and cycloalkyl Grignard reagents. The 2-substituted furans were used for the preparation of novel C1 substituted benzoxanorbornadiene and oxanorbornadienes.