No description available.

La preparación de nuevos ligandos quirales P-OP (fosfina-fosfinitos y fosfina-fosfitos), fácilmente preparados con una estrategia sintética en dos etapas desde una aproximación covalente, es descrita en la presente Tesis Doctoral. El mejor catalizador de la serie ha demostrado tener propiedades catalíticas excelentes en la hidrogenación asimétrica catalizada por rodio de una amplia variedad de olefinas funcionalizadas. El resultado excelente y el diseño modular de los ligandos sintetizados hacen éstos muy atractivos para futuras aplicaciones.La presente Tesis Doctoral describe también la preparación de nuevos ligandos quirales que pueden comportarse como catalizadores supramoleculares inspirados en el mecanismo de regulación alostérica de los enzimas. / A library of enantiomerically pure P-OP ligands (phosphine-phoshinites and phosphine-phosphites) straightforwardly available in two synthetic steps from enantiopure Sharpless epoxy ethers is reported in the present PhD. Thesis. The "lead" catalyst of the series has proven to have outstanding catalytic properties in the rhodium-catalysed asymmetric hydrogenation of a wide variety of functionalised alkenes. Their excellent performance and modular design makes them attractive for future applications.This PhD. Thesis also reports the development of a practical route to chiral diphosphine ligands with supramolecular motifs, with potential for allosteric modulation, which we prepared for future catalytic studies.

Group 9 transition metal pincer complexes have shown tremendous utility in a variety of E-H (E = main group element) bond activation reactions. In an effort to access new types of highly reactive pincer-like transition metal complexes this research focuses on the development of new late metal complexes supported by tridentate bis(phosphino)silyl ligands of the type [?3-(2-R2PC6H4)2SiMe]- ([R-PSiP]; R = Cy, iPr). The incorporation of a strongly electron donating and highly trans-labilizing silyl group at the central anionic position may promote the formation of new coordinatively unsaturated compounds capable of enhanced reactivity. In this regard, the synthesis of coordinatively unsaturated Rh and Ir complexes supported by R-PSiP ligation and their ability to activate E-H bonds will be detailed. The synthesis of Cy-PSiP ligated Rh and Ir species and the ability to access the products of N–H bond oxidative addition with these species was investigated. Both [Cy-PSiP]Rh and [Cy-PSiP]Ir complexes were shown to form isolable complexes of the type [Cy-PSiP]M(H)(NHR) (M = Rh, R = aryl; M = Ir, R = H, aryl). However, attempts to generate such amido hydride complexes by N-H activation of the corresponding amine led to divergent reactivity, where adducts of the type [Cy-PSiP]Rh(NH2R) were obtained for Rh, while N-H bond oxidative addition was observed for Ir to form the targeted amido hydride complexes, including a rare example of ammonia N-H bond oxidative addition to form a monomeric, terminal parent amido complex that was crystallographically characterized. Due to the scarcity of transition metal complexes that are capable of N-H bond oxidative addition, a thorough investigation of the N-H bond activation mediated by [Cy-PSiP]Rh and Ir with various N-H containing substrates, including alkyl amines, hydrazine derivatives, and benzamides was initiated. Extension of this reactivity to the related diisopropylphosphino derivative [iPr-PSiP]IrI was also probed, as the resulting complexes were envisioned to be less susceptible to potential cyclometalation processes. Indeed, oxidative addition of primary alkyl amines, hydrazines, and benzamides was observed for [R-PSiP]Ir. These results comprise an unprecedented example of a metal complex that is capable of facile N-H bond activation in such a wide range of substrates, including challenging substrates such as ammonia and alkyl amines. A rare example of Rh-mediated N-H oxidative addition was also observed for the reaction of [Cy-PSiP]RhI with benzophenone hydrazone. The potential for these [R-PSiP]Ir(H)(NHR) complexes to insert unsaturated substrates was investigated, as the development of new pathways for the formation of C-N bonds via transition metal catalyzed N-H bond oxidative addition to a metal center followed by insertion of an alkene or alkyne into the M-N or M-H bond may provide a new pathway for accessing intermolecular amination reactions. Insertion chemistry attempts with various alkenes, alkynes, allenes, C=O and C?N containing compounds is described. Lastly, the synthesis of IrIII complexes of the type {[R-PSiP]IrR'}+X? (R = Cy, iPr; R’ = H, Me; X = OTf, BF4, B(C6F5)4) and their interactions with the C-H bonds of arenes and aldehydes, as well as, the Si-H bonds of hydrosilanes is detailed. The Si-H bond activation chemistry observed was typically influenced by the counter anion X. Thus, the more coordinating anions OTF and BF4 were shown to coordinate to and stabilize the highly electrophilic Si in transiently generated Ir silylene species.

No description available.

The products of organic synthesis affect countless aspects of our everyday lives, from our medicines to our fuels, plastics and more. The discovery of new methods for organic synthesis is of paramount importance if we are to find greener and more efficient ways to synthesize commodity and fine chemicals, and lower the impact of the chemical industry on our environment. The aim of my doctoral thesis is to discover fundamentally new enantioselective transformations using transition metal catalysis, which can be applied to the synthesis of pharmaceutical agents, natural products or other fine chemicals. Hydroacylation is the atom economical addition of an aldehyde C–H bond across an unsaturated functional group such as an olefin or ketone. Theoretical studies on an intramolecular ketone hydroacylation catalyzed by rhodium were performed. The insights gained from this mechanistic study were then applied to the development of an asymmetric olefin hydroacylation using ethers, sulfides and sulfoxides as directing groups. Motivated by a desire to discover new catalysts with high activity and selectivity in rhodium catalyzed transformations, a chiral tridentate sulfoxide ligand was designed and synthesized. This ligand was found to be highly enantioselective in rhodium catalyzed 1,4-addition reactions. The use of allylic sulfoxides in a dynamic kinetic resolution was then investigated. The sulfoxide was found to direct a rhodium catalyzed olefin hydrogenation with simultaneous substrate racemization through a rhodium π-allyl pathway. Progress was made towards the total synthesis of a complex polyketide natural product, 6-deoxyerythronolide B. The key macrocyclization step was achieved in a model system by ring closing metathesis, and future work will be directed at completing the synthesis of the natural product.

The products of organic synthesis affect countless aspects of our everyday lives, from our medicines to our fuels, plastics and more. The discovery of new methods for organic synthesis is of paramount importance if we are to find greener and more efficient ways to synthesize commodity and fine chemicals, and lower the impact of the chemical industry on our environment. The aim of my doctoral thesis is to discover fundamentally new enantioselective transformations using transition metal catalysis, which can be applied to the synthesis of pharmaceutical agents, natural products or other fine chemicals. Hydroacylation is the atom economical addition of an aldehyde C–H bond across an unsaturated functional group such as an olefin or ketone. Theoretical studies on an intramolecular ketone hydroacylation catalyzed by rhodium were performed. The insights gained from this mechanistic study were then applied to the development of an asymmetric olefin hydroacylation using ethers, sulfides and sulfoxides as directing groups. Motivated by a desire to discover new catalysts with high activity and selectivity in rhodium catalyzed transformations, a chiral tridentate sulfoxide ligand was designed and synthesized. This ligand was found to be highly enantioselective in rhodium catalyzed 1,4-addition reactions. The use of allylic sulfoxides in a dynamic kinetic resolution was then investigated. The sulfoxide was found to direct a rhodium catalyzed olefin hydrogenation with simultaneous substrate racemization through a rhodium π-allyl pathway. Progress was made towards the total synthesis of a complex polyketide natural product, 6-deoxyerythronolide B. The key macrocyclization step was achieved in a model system by ring closing metathesis, and future work will be directed at completing the synthesis of the natural product.

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2008. / Includes bibliographical references.

Thesis (Ph.D.)--University of Delaware, 2008. / Principal faculty advisor: Douglass F. Taber, Dept. of Chemistry & Biochemistry. Includes bibliographical references.

Th. Doct.-ing.--Sc. pétrolières--Paris--École nationale du pétrole et des moteurs, 1985. / Notes bibliogr.

Proefschrift Rijksuniversiteit Groningen. / Met lit.opg. - Met samenvatting in het Nederlands.