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This thesis details the synthesis and characterisation of s-block metal (lithium, sodium and magnesium) phosphonium ylide, R(_3)PCHR', and iminophosphorane complexes, R(_3)PNR', together with some related phosphine oxide, R(_3)PO, and sulfide, R(_3)PS, species, where R= Ph or Me(_2)N and R' = H, Me or Ph. The first three chapters of the thesis provide an introduction to the topic, with details of the experimental methods employed and results obtained. Chapter 4 presents a systematic study of Lewis base complexed s-block metal aryloxides, (ArOM L)(_2) where Ar = C(_6)H(_3)Ph(_2) or MeC(_6)H(_2)((^1)Bu)(_2), L = R(_3)PCHR', R(_3)PNR', R(_3)PO or R(_3)PS, and M = Li, Na, and (ArO)(_2)Mg(L)(_2) where Ar = MeC(_6)H(_2)(^1)Bu)(_2) and L = R(_3)PCHR’ or R(_3)PNR'. This includes a discussion of the single crystal XRD structures of the eight neutral ligands used, L, and ten new complexes containing either lithium or sodium. Chapter 5 describes the application of some related s-block metal ylide complexes, e.g. Ph(_3)PCHMe-LiN(CH(_2)Ph(_2))(_2) and Ph(_3)PCHMe-NaN(SiMe(_3))(_2), to the Wittig reaction, together with some solution-state and solid-state discussions (two single crystal XRD structures) of s-block metal amide-phosphonium ylide complexes, R(_3)PCHR'.MNR'(_2) where R = Ph or Me(_2)N, R’ = H or Me, and R" = SiMe(_3) or CH(_2)Ph Chapter 6 details a range of N-s-block metallated iminophosphorane complexes (e.g. Ph(_3)PNLi-LiBr.2thf and R(_3)PNMgX-L where R = Ph or Me(_2)N and L = Lewis base) their application to transmetallation reactions with copper(I) compounds, solution-state and solid-state NMR studies and six new single- crystal XRD structures. Chapter 7 describes some very recent work involving alkyldiphenylphosphonium ylides, MePh(_2)PCHPh, and imines, MePh(_2)PNPh, including a single crystal XRD structural study of the latter and three of its lithium derivatives, e.g. [CH(_2)LiPh(_2)PNPh](_4). Chapter 8 is concerned with a number of unexpected results, including the synthesis, solid-state structure and proposed mechanism of a novel A^-phosphino- iminophosphorane, Ph(_2)(C(_3)H(_4)Ph)PNP(C(_3)H(_5))Ph, and two aminophosphonium salts, [R(_3)PNH(_2)](^+)[OC(_6)H(_3)Ph(_2)]" where R = Ph or Me(_2)N.

Photocopy of typescript

published_or_final_version / Chemistry / Master / Master of Philosophy

A range of substituted l,3-dithiol-2-ylidene systems have been prepared. These species have, subsequently, been converted to nitroso derivatives. The role of the 4-, 5- and ylidene subtituents in stabilising the nitroso-alkene moiety thus obtained has been investigated. X-ray molecular crystal data which show that these species are stabilised by intramolecular interactions are presented. Conversion of the nitroso derivatives to their thionitroso analogues has been attempted, but was unsuccessful. A selection of l-(l,3-dithiol-2-ylidene)-prop-2-ene systems have been prepared. These systems have been shown to be sufficiently activated to undergo nitrosation reactions at the 3-vinyl positon, though the nitroso-alkenes thus formed are unstable. A new route to 4,5-dicarbomethoxy-2-(tributylphosphino)-l,3-diselenolium tetrafluoroborate utilising hydrogen selenide as the source of selenium has been detailed. This Wittig reagent has been employed in the synthesis of various 1,3-diselenol-ylidene systems. Conversion to nitroso derivatives has been accomplised and X-ray data shows that the resultant nitroso-alkenes are stabilised by an intramolecular oxygen—selenium interaction.

Photocopy of typescript / v, 182 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Organic Chemistry, 1981

Thesis (Ph.D.) -- University of Adelaide, Dept. of Organic Chemistry, 1981. / Photocopy of typescript.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1992. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Made available in DSpace on 2014-06-12T23:13:46Z (GMT). No. of bitstreams: 2 arquivo4229_1.pdf: 4650132 bytes, checksum: 934ddae6e81960a4feab0a121885d332 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2009 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Os trifluoroboratos orgânicos têm demonstrado grande aplicabilidade, especialmente devido a sua facilidade de preparação e a sua versatilidade na formação de novas ligações carbono-carbono. Estes compostos podem ser preparados a partir de materiais de baixo custo e são estáveis ao ar, podendo ser estocados por longos períodos sem apresentar degradação. A primeira parte deste trabalho descreve um estudo através de Ressonância Magnética Heteronuclear, onde diversos trifluoroboratos orgânicos foram analisados através de RMN de 1H , 13C , 19F e 11B. Pela primeira vez foi observada a ressonância para o átomo de carbono ligado ao átomo de boro para a maior parte dos trifluoroboratos analisados. Adicionalmente, uma modificação na seqüência de pulso para RMN de 11B foi utilizada, permitindo a observação das constantes de acoplamento 11B- 19F para alguns compostos. Na segunda etapa do trabalho foi desenvolvida uma nova metodologia para a preparação de alquenos funcionalizados com a função trifluoroborato a partir da reação de formil-trifluoroboratos de arila e fosforanas estabilizadas. A reação apresentou diversas vantagens como utilizar água como solvente e os produtos foram obtidos em bons rendimentos sem a necessidade de purificação posterior. Apesar da reação levar preferencialmente ao isômero E, a diastereosseletividade da reação mostrou-se dependente das condições reacionais, do tempo de reação e do tipo de substrato empregado. A última etapa deste trabalho descreve um estudo toxicológico e um efeito farmacológico de um trifluoroborato orgânico. Os resultados revelaram que 2-tiofenotrifluoroborato de potássio, oralmente administrado, reduziu dor visceral induzida por ácido acético administrado intraperitoniamente. O pequeno potencial tóxico do composto avaliado foi evidenciado primeiramente pelo fato de que todos os animais permaneceram vivos após 72h da administração. Adicionalmente, a administração de 2-tiofenotrifluoroborato de potássio não produziu nenhuma evidência de dano hepático ou renal considerando os parâmetros bioquímicos avaliados

This thesis is primarily focused on the development of Wittig methodologies and the applications of the product alkenes in organocatalysis and drug discovery. Herein is described an aqueous Wittig methodology for the synthesis of α-methylstilbenes and their use in the preparation of novel triazole stilbene inhibitors of aromatase, a clinically validated target for the treatment of estrogen receptor positive breast cancer. As well, a one-step, stereoselective synthesis of alkenyl phenols was developed. The method provides easy access to a variety of compounds that contain this synthetically and biologically important functionality, including natural product phenolic stilbenes. In turn, alkenyl phenols were used as a key component in a novel organocatalytic methodology for the synthesis of cyclobutanes in good yields and high enantioselectivity. Notably, this is one of relatively few asymmetric, catalytic methods for cyclobutane synthesis. Preliminary biological activity of some of these cyclobutane derivatives is reported, including promising anti-cancer activity. Finally, a ten-step total synthesis of the Amaryllidaceae alkaloid (+)-trans-dihydronarciclasine was completed. The synthesis features an organocatalytic Michael-aldol cascade on a cinnamaldehyde derivative, which was prepared using a Wittig methodology previous reported by the McNulty group. Importantly, this compound was found to be one of the most potent anti-Zika compounds reported to date. Future work should focus on improving the potency and selectivity of the various aforementioned chemotherapeutics, with concurrent efforts to build upon the novel methodologies discussed herein. / Thesis / Doctor of Philosophy (PhD) / The Wittig reaction is one of the best ways to make alkenes, a type of reactive bond between two carbon atoms. A new Wittig reaction was developed and used in the preparation and discovery of potent inhibitors of aromatase, an enzyme responsible for the proliferation of many breast cancers. As well, another Wittig methodology was created for the straightforward synthesis of an otherwise difficult to prepare class of alkenes. In turn, these types of alkenes were used in a novel preparation of cyclobutanes, a chemical structure that is difficult to make but can impart useful properties to drugs and materials. Finally, a Wittig reaction previously reported by the McNulty group was used as part of a chemical synthesis of trans-dihydronarciclasine, a rare natural product isolated from daffodils. Trans-dihydronarciclasine was discovered to have antiviral activity and is one of the most potent inhibitors of the Zika virus discovered to date.