Irradiation of a tryptamine linked through its side-chain nitrogen to an alkylidene malonate residue results in an intramolecular [2 + 2] cycloaddition to the indole 2,3-double bond. The resultant cyclobutane undergoes spontaneous retro-Mannich fission to produce a spiro[indoline-3,3-pyrrolenine] with relative configuration defined by the orientation of substituents in the transient cyclobutane. The novel tandem intramolecular photocycloaddition- retro-Mannich (TIPCARM) sequence leads to a spiropyrrolidine which is poised to undergo a second retro-Mannich fragmentation [TIPCA(RM)₂] that expels the malonate unit present in the photo substrate and generates transiently an indolenine. The indolenine undergoes rearrangement to a β-carboline which can undergo further rearrangement under oxidizing conditions to an oxindole. Three oxindole natural products, coerulescine, horsfiline and elacomine, were synthesized using this strategy. The TIPCARM strategy was extended to an approach that would encompass the Vinca alkaloids vindorosine and minovine. In this case, the TIPCARM sequence was followed by an intramolecular cyclization that provided tetracyclic ketone 5.86 containing rings A, B, C and D of vindorosine. A tetracyclic intermediate was synthesized which could also provided access to the Vinca alkaloid minovine. / Graduation date: 2012

Chemical biology encompasses the study and manipulation of biological system using chemistry, often by virtue of small molecules or unnatural amino acids. Much insight has been gained into the mechanisms of biological processes with regards to protein structure and function, metabolic processes and changes between healthy and diseased states. As an ever expanding field, developing new tools to interact with and impact biological systems is an extremely valuable goal. Herein, work is described towards the synthesis of a small library of heterocyclic-containing small molecules and the mechanistic details regarding the interesting and unexpected chemical compounds that arose; an alternative set of non-toxic copper catalyzed azide-alkyne click conditions for in vivo metabolic labelling; and the synthesis of an unnatural amino acid for further chemical modification via [3+2] cycloadditions with nitrones upon incorporation into a peptide of interest. Altogether, these projects strive to supplement pre-existing methodology for the synthesis of small molecule libraries and tools for metabolic labelling, and thus provide further small molecules for understanding biological systems.

Chemical biology encompasses the study and manipulation of biological system using chemistry, often by virtue of small molecules or unnatural amino acids. Much insight has been gained into the mechanisms of biological processes with regards to protein structure and function, metabolic processes and changes between healthy and diseased states. As an ever expanding field, developing new tools to interact with and impact biological systems is an extremely valuable goal. Herein, work is described towards the synthesis of a small library of heterocyclic-containing small molecules and the mechanistic details regarding the interesting and unexpected chemical compounds that arose; an alternative set of non-toxic copper catalyzed azide-alkyne click conditions for in vivo metabolic labelling; and the synthesis of an unnatural amino acid for further chemical modification via [3+2] cycloadditions with nitrones upon incorporation into a peptide of interest. Altogether, these projects strive to supplement pre-existing methodology for the synthesis of small molecule libraries and tools for metabolic labelling, and thus provide further small molecules for understanding biological systems.

Le ligand nacnacxylH (xyl = C6Me2H3) et les ligands dikétimines N-alkyle substitués (nacnacCH(Me)PhH, nacnacBnH and nacnaciPrH) ont été préparés avec de bons rendements à l’exception du nacnaciPrH (23%) en utilisant un protocole en une étape et à l’aide d’un montage Dean-Stark. La réaction du S,S-nacnacCH(Me)PhH et du nacnacBnH avec le nBuLi dans le THF conduit au S,S-nacnacCH(Me)PhLi(THF) et au nacnacBnLi(THF). Les tentatives de bromation de ces composés par le N-bromosuccinimide conduisent plutôt aux ligands S,S-succnacnacCH(Me)PhH et succnacnacBnH (succ = succinimido) substitués par un groupement succinimido sur le carbone  La chloration par le N-chlorosuccinimide conduit au produit désiré, mais avec des impuretés. La réaction de ces ligands avec le CuOtBu (ou bien MesCu, où Mes = C6Me3H2, et une quantité catalytique de CuOtBu) en présence de bases de Lewis donne les (nacnacxylCu)2(-toluène), nacnacxylCuCNC6H3(Me)2, nacnacCH(Me)PhCuL (L = PPh3, PMe3, CNC6H3(Me)2, DMAP, lutidine, Py, MeCN), nacnacBnCuL (L = PPh3, CNC6H3(Me)2, styrène, trans-stilbene, phenylvinylether, acrylonitrile, diphenylacetylène), nacnaciPrCuL (L = PPh3, CNC6H3(Me)2, MeCN) et le succnacnacCH(Me)PhCuL (PPh3, CNC6H3(Me)2, pyridine). Tous ces complexes sont jaunes et sensibles à l’air et à l’humidité. En l’absence de fortes bases de Lewis, on n’observe pas de réaction entre les précurseurs de cuivre et les ligands N-alkyle substitués. Les études RMN des complexes dans le C6D6 ne présentent pas de complexe de toluène mais un mélange à l’équilibre du (nacnacxylCu)2(-C6D6) et nacnacxylCu(C6D6) dans une proportion de 2 pour 1. Alors que l’addition de plus de cinquante équivalents soit de THF, soit de toluène n’induit aucun changement des spectres RMN, l’addition de 2 équivalents de MeCN conduit instantanément au complexe nacnacxylCu(MeCN). De plus, le (nacnacxylylCu)2(-C6D6) ne se coordone ni ne réagit avec le N2O, même après avoir été chauffé à 60°C pendant treize jours. En présence de DPA (diphenylacétylène), la réaction du nacnacBnH avec le CuOtBu conduit au dimère ponté (nacnacBnCu)2(µ-DPA). L’addition d’un excès de DPA (10-12 équivalents) transforme le dimère ponté en complexe lié en position terminale nacnacBnCuDPA. Les nacnacRH (R = CH(Me)Ph et i-Pr) ne forment pas de complexe ni avec les oléfines ni avec le DPA. Une réactivité similaire a été observée avec les complexes de nacnacCH(Me)PhCu(NCMe) et nacnaci-PrCu(NCMe). Tandis que le complexe lié en position terminale par MeCN a été isolé et caractérisé, l’équilibre en solution nous laisse suspecter la formation d’un complexe d’acétonitrile ponté. Des études de réactivité comparatives ont été menées sur quelques complexes de cuivre. La Morpholine ne réagit pas avec le nacnacBnCu(acrylonitrile) contrairement à l’acrylonitrile libre. L’expérience de l’échange d’oléfine montre que l’acrylonitrile (une oléfine électro-attractrice) se lie plus fortement que les autres oléfines, mettant ainsi en évidence l’importance de la rétrodonation  face à la donation La rétrodonation est cependant faible comparée aux autres complexes de styrène structurellement caractérisés. Les complexes nacnacCH(Me)PhCuL (L = PPh3 et MeCN) ont été employés dans la cyclopropanation catalytique du styrène et dans l’addition conjuguée du ZnEt2 sur la 2-cyclohexénone, mais les résultats indiquent que le ligand dikétimine est éliminé avant son entrée dans le cycle catalytique. Par conséquent, il n’y a pas d’induction chirale. Les complexes tétra coordinées de cuivre avec les nacnacRCu(phen) (R = Bn, CH(Me)Ph et Phen = 1,10-phenanthroline, 2-Mes-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline (dmp) et 2,9-diphenyl-1,10-phenanthroline (dpp)) ont été synthétisés. Ces complexes sont d’une intense couleur bleue et des interactions d’empilement entre l’un des cycles phényle des ligands nacnac et la phénanthroline ont été observées dans les structures à l’état solide. Les mesures en absorption UV-visible ont été effectuées dans le toluène et les bandes MLCT sont déplacées vers le rouge par rapport à celles des complexes de cuivre et bisphénanthroline. Tous ces composés émettent à l’état solide mais les complexes 1,10-phenanthroline et 2-Mes-1,10-phenanthroline n’émettent pas en solution. Pour renforcer les interactions d’empilement , les nouveaux ligands nacnacRH (R = CH2C6H2(OMe)3, CH2C6F5) et leurs complexes de cuivre respectifs ont été préparés avec du dmp et dpp. Afin de permettre la comparaison, le nacnaciBuCu(dmp) a été synthétisé. Alors que les complexes dmp montrent une augmentation des interactions intramoléculaires - avec les substituants phényle du ligand dikétimine et de la phénanthroline, les complexes dpp ne révèlent pas de telles interactions. Les complexes perfluorés montrent, en absorption et en émission, un déplacement significatif vers le bleu, alors que les complexes substitués par un groupements isobutyle présentent des transitions déplacées vers le rouge. Alors que les intensités de luminescence et les durées de vie sont faibles, les déplacements réduits de Stokes et les pics étroits de luminescence comparables indiquent une réduction des distorsions de l’état excité. / The ligand nacnacxylH (xyl = C6Me2H3) and the N-alkyl substituted diketimine ligands (nacnacCH(Me)PhH, nacnacBnH and nacnaciPrH) have been prepared in good yields except nacnaciPrH (23%) using a one-step procedure with the help of a Dean-Stark apparatus. Reaction of S,S-nacnacCH(Me)PhH and nacnacBnH with nBuLi in THF gave S,S-nacnacCH(Me)PhLi(THF) and nacnacBnLi(THF). Attempts to brominate these THF adducts with N-bromosuccinimide gave instead the -carbon substituted succinimido ligands S,S-succnacnacCH(Me)PhH and succnacnacBnH (succ = succinimido). Chlorination with N-chlorosuccinimide, afforded the desired product albeit with significant amounts of impurities. Reaction of these ligands with CuOtBu (or MesCu and catalytic amounts of CuOtBu, Mes = C6Me3H2) in the presence of Lewis bases gave (nacnacxylCu)2(-toluene), nacnacxylCuCNC6H3(Me)2, nacnacCH(Me)PhCuL (L = PPh3, PMe3, CNC6H3(Me)2, DMAP, lutidine, Py, MeCN), nacnacBnCuL (L = PPh3, CNC6H3(Me)2, styrene, trans-stilbene, phenylvinylether, acrylonitrile, diphenylacetylene), nacnaciPrCuL (L = PPh3, CNC6H3(Me)2, MeCN) and succnacnacCH(Me)PhCuL (PPh3, CNC6H3(Me)2, pyridine). All complexes are yellow and sensitive to air and moisture. There was no reaction between the copper precursors and the N-alkyl substituted ligands in the absence of strong Lewis bases. NMR studies of the complex (nacnacxylCu)2(-toluene) in C6D6, showed no toluene adduct but an equilibrium mixture of (nacnacxylCu)2(-C6D6) and nacnacxylCu(C6D6) in a ratio of 2:1. While addition of up to 50 equiv of either toluene or THF did not cause any significant change in the 1H NMR spectrum, addition of 2 equiv MeCN gave instantaneously the nacnacxylCu(MeCN) complex. In addition, (nacnacxylylCu)2(-C6D6) did not coordinate or react with N2O even after heating at 60 oC for thirteen days. In the presence of DPA (diphenylacetylene), reaction of nacnacBnH with CuOtBu yields the bridged dimer (nacnacBnCu)2(µ-DPA). Addition of excess DPA (10-12 equiv) converts the bridged dimer to the terminally bound complex nacnacBnCuDPA. NacnacRH (R = CH(Me)Ph and i-Pr) did not form complexes with olefins or with DPA. Similar reactivity was observed in nacnacCH(Me)PhCu(NCMe) and nacnaci-PrCu(NCMe) complexes. While the terminally bound MeCN complex was isolated and characterized, equilibrium in solution led us to suspect the formation of a bridged acetonitrile adduct. Reactivity and comparative studies were performed with several copper complexes. Morpholine did not react with nacnacBnCu(acrylonitrile) while free acrylonitrile does. Olefin exchange experiment showed that acrylonitrile (an electron withdrawing olefin) binds stronger than the other olefins examined, showing the importance of -backbonding relative to -donation. -Backbonding is, however, still low when compared other structurally characterized transition metal styrene complexes. Complexes nacnacCH(Me)PhCuL (L = PPh3 and MeCN) have been employed in catalytic cyclopropanation of styrene and the conjugate addition of ZnEt2 to 2-cyclohexenone, but results indicate that the diketimine ligand is lost before it enters the catalytic cycle. Hence, there was no chiral induction. Four-coordinate copper(I) complexes of the form nacnacRCu(phen) (R = Bn, CH(Me)Ph and Phen = 1,10-phenanthroline, 2-Mes-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline (dmp) and 2,9-diphenyl-1,10-phenanthroline (dpp)) were also prepared. The complexes are intensely blue in colour and intramolecular -stacking interactions between one of the phenyl rings of nacnac ligand with the phenanthroline were observed in the solid state structures. UV-vis absorption measurements were performed in toluene and the MLCT bands are red-shifted relative to those of bisphenanthroline copper complexes. All compounds are emissive in the solid state, but 1,10-phenanthroline and 2-Mes-1,10-phenanthroline complexes do not emit in solution. To buttress the -stacking interactions, the new ligands nacnacRH (R = CH2C6H2(OMe)3, CH2C6F5) and their respective copper complexes with dmp and dpp were prepared. For the sake of comparison, nacnaciBuCu(dmp) was prepared. While the dmp complexes showed enhanced -intramolecular interactions with both phenyl substituents of the diketimine ligand and the phenanthroline, dpp revealed no such interactions. The perfluorinated complex showed a significant blue-shift in absorption and emission spectra when compared to the other complexes, while the isobutyl substituted complex displayed red-shifted transitions. While luminescence intensities and lifetimes were low, reduced Stoke shifts and comparable sharp luminescence peaks indicate reduced distortions in the excited state.

Natural products are essential tools for basic cellular studies leading to the identification of medically relevant protein targets and the discovery of potential therapeutic agents. We have developed a set of second generation diazo reagents with small steric footprints, namely an alpha-trifluoroethyl (HTFB) diazo reagent, for simultaneous arming and SAR studies of bioactive natural products. The Rh(II)-catalyzed O-H insertions of several alcohol-containing natural products, including the potent translation inhibitor lactimidomycin, are investigated and useful reactivity and both chemo- and site- (chemosite) selectivities are observed. The alpha-trifluoroethyl diazo reagents (HTFB) shows clear differences in the IL-2 reporter assay with FK506 derivatives and provides greater retention of biological activity in a hMetAP2 proliferation assay of fumagillol derivatives compared to the first generation pbromophenyl diazo reagent (HBPA). The synthetic utilities of the new alpha-trifluoroethyl diazo reagent (HTFB) provide a great new tool for basic cellular studies facilitating the discovery of new drug candidates for human disease. Furthermore, we are interested in methodologies for beta-lactone synthesis and transformations. In this study, we demonstrated synthetic versatilities of beta-lactones for the synthesis of beta-lactam congeners of orlistat as fatty acid synthase inhibitors via SnCl4- promoted tandem Mukaiyama aldol-lactonization (TMAL) reaction and a one-pot, mild conversion of beta-lactones to beta-lactams. The inhibitory activities of the derived beta-lactam derivatives are determined in a biochemical fluorogenic assay using recombinant FASTE, and the micro-molar range FAS-TE inhibitory activities were observed. Additionally, we pursued synthetic studies toward the total synthesis of spongiolactone, which is a unique beta-lactone-containing marine diterpenoid, isolated from the marine sponge Spongionella gracilis. This natural product bears a unique tricyclic beta-lactone core possessing four contiguous stereogenic centers and an additional stereogenic quaternary carbon on a cyclohexyl appendage. We completed the total synthesis of 6,15-bis-epi-spongiolactone by employing an intramolecular nucleophilecatalyzed aldol-lactonization (NCAL) process as the key step to construct the fused tricyclic beta-lactone core. Importantly, we developed a double diastereoselective and, for the first time, a kinetic resolution via the NCAL process that enables an enantioselective strategy to the tricyclic beta-lactone core of (+)-spongiolactone.

Carbo- and heterocyclic compounds are of great interest to chemists. Intramolecular cyclization strategies of donor-acceptor (D-A) cyclopropanes and alkylidene malonate monoamides have excellent potential for synthesis as they offer easy access to structurally-diverse compounds. The work described in this thesis accesses the scope of the In(OTf)3-catalyzed cyclization reaction of cyclopropanes and alkylidene malonate monoamides. In(OTf)3-catalyzed reactions of alkenyl and heteroaryl cyclopropyl ketones were examined in the synthesis of functionalized cyclohexenone-based derivatives (Chapter 2). Subsequent efforts to utilize a tandem cyclopropane ring-opening/Friedel-Crafts alkylation sequence of methyl 1-(1H-indolecarbonyl)-1-cyclopropanecarboxylates to prepare functionalized hydropyrido[1,2-a]indole-6(7H)-ones is discussed in Chapter 3. The extension of this tandem protocol towards the total synthesis of (±)-deethyleburnamonine is the subject of Chapter 6. Intramolecular Friedel-Crafts alkylation of N-indolyl alkylidene malonate monoamides was also examined. An In(OTf)3-catalyzed cyclization of substituted methyl 2-(1H-indole-1-carbonyl) acrylates afforded a series of 1H-pyrrolo[1,2-a]indole-3(2H)-ones (Chapter 4), whereas substrates with the indole 2-position blocked provided access to substituted 4H-pyrrolo[3,2,1-ij]quinolin-4-ones (Chapter 5).

Chemical biology encompasses the study and manipulation of biological system using chemistry, often by virtue of small molecules or unnatural amino acids. Much insight has been gained into the mechanisms of biological processes with regards to protein structure and function, metabolic processes and changes between healthy and diseased states. As an ever expanding field, developing new tools to interact with and impact biological systems is an extremely valuable goal. Herein, work is described towards the synthesis of a small library of heterocyclic-containing small molecules and the mechanistic details regarding the interesting and unexpected chemical compounds that arose; an alternative set of non-toxic copper catalyzed azide-alkyne click conditions for in vivo metabolic labelling; and the synthesis of an unnatural amino acid for further chemical modification via [3+2] cycloadditions with nitrones upon incorporation into a peptide of interest. Altogether, these projects strive to supplement pre-existing methodology for the synthesis of small molecule libraries and tools for metabolic labelling, and thus provide further small molecules for understanding biological systems.

L’obtenció de lligands quirals eficients i de fàcil accés segueix essent un dels objectius principals en catàlisi. Les fosfines estereogèniques voluminoses han mostrat ser molt eficients en un ampli ventall de reaccions catalítiques. No obstant, la seva síntesis de forma enantiomèricament pura és molt sovint complicada. Podem considerar que els mètodes més efectius per a la construcció de fòsfor estereogènic són els desenvolupats per Jugé i Evans basats en l’obertura d’oxazafosfolidines enantiopures i la desprotonació enantioselectiva de fosfino-borans, respectivament. Aquests mètodes, tanmateix, presenten limitacions i desavantatges. Aquest fet confereix atractiu al desenvolupament de nous processos per a la síntesi de fòsfor estereogènic. En la present tesi doctoral, es va estudiar la condensació de fenil i tert-butilfosfines amb el (cis)-1-amino-2-indanol. Aquestes ens conduí a les corresponents oxazafosfolidines amb bon rendiment i diastereoselectivitats de fins a 18 : 1. La condensació amb aquest aminoalcohol ens proporcionà oxazafosfolidines amb funció NH lliure. Justament aquesta nova funcionalitat s’ha revelat clau en la química d’obertura d’anells d’oxazafosfolidines. Pel que fa l’obertura d’anell de la 2-feniloxazafosfolidina amb organolítics, aquestes transcorregueren amb inversió o retenció depenent de la substitució sobre l’àtom de nitrogen. Quan tenim un grup NH, l’obertura transcorre amb inversió mentre que quan el nitrogen està substituït amb un metil s’observa retenció tal i com havia descrit Jugé i col•laboradors. En la mateixa línia, l’obertura d’anell de la 2-tert-butiloxazafosfolidina amb el grup NH lliure amb organomagnesians té lloc de forma totalment estereoselectiva a temperatures elevades amb inversió. També s’ha desenvolupat una obertura reductiva de la 2-tert-butiloxazafosfolidina mitjançant l’ús combinat d’una font d’hidrur i un magnesià. Aquesta obertura també és totalment estereoselectiva i no té precedents en la literatura. Els productes d’obertura de la 2-feniloxazafosfolidina es van hidrolitzar segons la metòdica descrita per Jugé a les corresponents metoxifosfines amb bons rendiments i elevats ee. Els productes d’obertura de la 2-tert-butiloxazafosfolidina amb grups alquil es van poder trencar de l’auxiliar quiral amb Li/NH3(liq.) obtenint-se les aminofosfines amb ee>99%. Alternativament, es va desenvolupar una seqüència d’eliminació i posterior hidròlisis que permet alliberar les aril-tert-butilaminofosfines amb bons rendiments i ee>99%. Aquests es va derivatitzar la tert-butilaminofosfina en diferents compostos. Finalment també es va descriure una nova família de lligands basats en fosfinosulfonamides. Es van descriure nous complexos de Rh-fosfinosulfonamida els quals es van aplicar a la reacció de cicloaddició [2+2+2] intramolecular de manera exitosa. Aquests complexos ens van permetre superar amb escreix els resultats descrits prèviament. Finalment, es va dissenyar una nova família de lligands que hem anomenat ThaxPHOS. Es van emprar aquests en la reacció de Pauson-Khand intermolecular catalítica enantioselectiva. La desprotecció i complexació amb dicobalt dóna molt bon resultats i bones diastereoselectivitats gràcies a equilibracions tèrmiques. Inicialment, es va dissenyar una estratègia estequiomètrica enantioselectiva per a l’obtenció de l’adducte de Pauson-Khand amb acetilè lliure sense emprar l’acetilè en forma de gas. L’aplicació d’aquests complexos en la reacció catalítica han donat els millors resultats mai descrits en aquest camp. S’ha plantejat un nou mecanisme catalític per justificar els resultats obtinguts. / The synthesis of efficient and easily affordable chiral ligands are one of the main goals in catalysis. Bulky stereogenic phosphine have demonstrated to be excellent ligands in a broad range of catalytic reactions. Furthermore, their synthesis in an optically pure form is usually difficult. We can consider that the method developed independently by Jugé and Evans are the most effective in this field. Nevertheless, these methods have some drawbacks. These downsides need to be improved and new synthetic methodologies need to be developed to obtain stereogenic phosphorus compounds. In this doctoral thesis we studied the condensation of phenyl- and tert-butylphosphines with (cis)-1-amino-2-indanol. These allowed us to obtain the corresponding oxazaphospholidines with excellent yields and diastereoselectivities (up to 18 : 1). These condensations allowed us to get a free NH functionality. We saw as this secondary amine was the key for our ring-opening strategy. Taking advantage of this group, we performed the ring-opening reaction allowing us to obtain the corresponding ring-opened product with inversion of configuration on the phosphorus atom. This reaction was carried out with total diastereoselectivity, and the ring-opened products obtained from 2-phenyloxazaphospholidine were hydrolyzed following the Jugé procedure described in literature. We obtained the corresponding methoxyphosphine with excellent yields and high ee. The ring-opened products obtained from 2-tert-butyloxazaphospholidine with alkyl groups were reductively cleaved with Li/NH3(l) affording the corresponding aminophosphine with ee>99%. Alternatively, we developed a new strategy based on elimination-hydrolysis to free the corresponding aryl-tert-butylaminophosphines with excellent results and optically pure. Subsequently, we described a new ligand family based on phosphinosulfonamide. We described new complexes of Rh-phosphinosulfonamide and we tested them in the intramolecular cycloaddition [2+2+2] significantly improving on the previous results described. Finally, we designed a new family of PnP* ligands called ThaxPHOS. These ligands were used in the enantioselective catalytic intermolecular Pauson-Khand reaction. The deprotection and successive coordination gave excellent yields and diastereoselectivities due to thermal equilibration. We used ThaxPHOS ligands in this reaction and we described the best results ever obtained in this field and we described a new catalytic mechanism to explain our results.

This thesis is comprised of two parts. The first part describes the synthesis of cyclopentadienyltungsten complexes containing a pendant alkyne group (I), and the subsequent photo-induced intramolecular coordination of the alkyne, forming complexes such as II. Compounds containing intramolecularly coordinated alkynes are rare, and this is the first example using cyclopentadiene as the core ligand. The second part describes the synthesis and structural characterisation of a number of novel metal complexes containing N-heterocyclic carbene ligands, some containing particular functionality for taylored applications. New methods were used to form complexes of rhodium, iridium, silver and gold (eg. III, IV). Structural and spectroscopic properties of the complexes were correlated with electronic characteristics of the ancillary ligands. A number of rhodium and iridium complexes (eg. IV) derived from imidazolium-linked cyclophanes were synthesised and structurally characterised. Complexes of N-heterocyclic carbenes with pendant ionic groups were synthesised, and a preliminary examination of their catalytic activity in water was performed. N-Heterocyclic carbenes complexes containing an electron withdrawing nitro group were synthesised and the effect of the nitro group on metal-ligand bonding was examined.

Diss. Linköping : Univ., 2004.