A presente tese teve como foco principal de trabalho acoplamentos cruzados carbono-carbono, especialmente os acoplamentos Heck, Suzuki e Sonogashira. Cada um dos acoplamentos foi trabalhado de maneira individual considerando algumas características tecnológicas relevantes à área. - Para o acoplamento Heck, foi estudado o sistema catalítico mais adequado ao acoplamento C-C entre um álcool alílico e um brometo de vinila. Com os resultados obtidos foi possível propor um mecanismo para a reação estudada bem como a modelagem dos parâmetros de reação para otimizar o rendimento do produto desejado. - Para o acoplamento Suzuki, foram desenvolvidos catalisadores a base de paládio e paládio/ouro suportados em sílica. Ambos catalisadores foram altamente ativos para a reação de Suzuki. O sistema catalítico desenvolvido, além de tudo, consiste no uso de um solvente ambientalmente correto – água – e a possibilidade de reuso, tanto do catalisador, quanto do meio reagente, torna esse processo bastante atrativo sob o ponto de vista da química verde. - Duas partes do trabalho se referem à funcionalização de uma matéria-prima consideravelmente barata e abundante – terpenos, substâncias de origem natural e constituintes principais de vários dos óleos essenciais naturais brasileiros. Primeiro foi estudado o acoplamento Heck entre terpenos e haletos de arila variados. Apesar de razoavelmente pouco reativos neste tipo de reação, os terpenos foram acoplados com auxílio do sistema catalítico adequado até que se obtivesse o máximo de rendimento do(s) produto(s) desejado(s). Os produtos de acoplamento obtidos nessa parte do trabalho podem ser utilizados como intermediários de síntese de moléculas mais complexas e com interesses científico-tecnológicos mais nobres. Por fim, os monoterpenos foram acoplados para a obtenção de compostos imidazólicos utilizados na obtenção de líquidos iônicos. O acoplamento seletivo entre alquinos baseados em monoterpenos e imidazoles halogenados mono e dissubstituídos foi estudado e o tipo de produto obtido abre uma janela de novas oportunidades sintéticas. Os produtos obtidos são líquidos iônicos e os dissubstituídos podem, ainda, serem utilizados como ligantes quirais. / This thesis focused on development of carbon-carbon cross-couplings systems, especially Heck, Suzuki and Sonogashira couplings. Each of these systems was worked individually considering some technological characteristics relevant to the area. - For the Heck coupling, the most suitable catalyst system was studied for C-C couplings between an allylic alcohol and a vinyl bromide. With these results we propose a mechanism for the reaction studied and the modeling of reaction parameters to optimize the yield of the desired product. - For the Suzuki coupling, catalysts based on palladium and palladium / gold supported on silica have been developed. Both were highly active catalysts for the Suzuki reaction. The catalyst system developed, above all, consists in the use of a solvent environmentally friendly - water - and the possibility of reusing both, the catalyst as well as the reaction medium makes this process very attractive from the point of view of a greener chemistry. - Two parts of this work refer to the functionalization of a raw material considerably cheap and abundant – terpenes, substances of natural origin and major constituents of many natural essential oils in Brazil. First we studied the Heck coupling between aryl halides and terpenes. Although fairly unreactive in this type of reaction, the terpenes could be coupled with the aid of a suitable catalytic system until achieving the maximum yield of the product(s) desired. The coupling products obtained in this part of the work can be used as intermediates for the synthesis of more complex molecules with scientific and technological nobler interest. Finally, the monoterpenes were coupled to obtain imidazole compounds used in the preparation of ionic liquids. The selective coupling of alkynes monoterpenes based and halogenated mono- and disubstituted imidazoles has been studied and the type of product opens a new window of synthetic opportunities. The resulting products are ionic liquids and the disubstituted products can also be used as chiral ligands.

No / A new method for the synthesis of meso-substituted porphyrins is described: reaction of 5,10,15,20-tetrabromoporphine magnesium complex with aryl or heteroaryl boronic acids in the presence of Pd(PPh3)4 gave meso-substituted porphyrins in yields up to 70%.

The stereochemical course of the Pd–catalyzed Suzuki-Miyaura cross-coupling of α-substituted, enantioenriched allylic boronic esters with phenyl iodide has been examined. The secondary boronic esters were prepared in both racemic and enantioenriched forms via borylationof a lithiated carbenoid with a geometrically defined vinyl boronic ester. The geometric purities were determined to be >99% and the enantiomeric excesses of stereodefined secondary boronic esters were found to exceed 98:2. In total, 8 allylic boronic esters were successfully cross-coupled, providing arylated products with high regioselectivities (>90:10) and complete enantiospecificities (>99%). The cross-coupling of a sterically and electronically unbiased, deuterated substrate confirmed that fully equilibrated π-allylic intermediates are not involved. Additionally, correlating the absolute configurations of the allylic boronic ester and the cross-coupling product allowed us to confirm that the transmetalation step of the reaction proceeded through a closed transition state via a syn-SE’ mechanism, which further suggests the importance of the distinct Pd-O-B bond linkage. Further, the cross-coupling of vinyl iodides to secondary boronic esters was investigated. / Thesis (Master, Chemistry) -- Queen's University, 2013-11-12 19:05:19.488

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Student Number : 9201775F - MSc dissertation - School of Chemistry - Faculty of Science / The base/light-induced cyclisation (condensation) reaction between alkyl and carbonyl substituents on biaryl compounds discovered in the University of the Witwatersrand laboratories was used to synthesise benzo[c]carbazoles. Specifically, 5,7-dimethyl-7H-benzo[c]carbazole was synthesised from 2-methyl-1H-indole in 79 % yield over four steps. The reaction sequence involved bromination of 2-methyl-1H-indole at C-3 to give 3-bromo-2-methyl-1H-indole. The subsequent methylation of the amino group to give 3-bromo-1,2-dimethyl-1H-indole was followed by Suzuki coupling with acetophenone-2-boronic acid under non-aqueous reaction conditions to give 1-[2-(1,2-dimethyl-1H-indol-3-yl)phenyl]. Lastly, tBuOK/hν–induced cyclisation of the product yielded the desired benzo[c]carbazole. 10-Methoxy-5,7-dimethyl-7H-benzo[c]carbazole was synthesized analogously in 75% yield from 5-methoxy-2-methyl-1H-indole.

Thesis advisor: James P. Morken / The Suzuki-Miyaura cross-coupling reaction is a common strategy for the formation of a new carbon-carbon bond in organic synthesis. However, intramolecular coupling of allylboron ester and aryl electrophiles has never been reported. Herein, Pd-catalyzed intramolecular cross-coupling of allylboronic pinacol ester and vinyl or aryl bromides is presented. Pt-catalyzed 1,2-diboration of 1,3-dienes give α-chiral bis-allylboronic esters, which can undergo diastereoselective additions to carbonyl electrophiles tethered to vinyl or aryl halides to generate a new allylboronic ester moiety. Under Suzuki coupling conditions, the allylboronic esters moiety and the vinyl bromides in the allylation products can cross-couple in an intramolecular fashion to afford highly substituted four-, five-, and six-membered rings with excellent yields and moderate diastereoselectivity. / Thesis (MS) — Boston College, 2014. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Este trabalho descreve o estudo da reação de acoplamento de Suzuki do brometo de vinila e do (E)-bromoestilbeno com ácidos arilborônicos empregando precursores catalíticos de níquel. Um sistema catalítico eficiente para a síntese de estireno foi desenvolvido, por meio da reação de acoplamento de Suzuki catalisada pelo complexo NiCl2(PPh3)2, atingindo-se ótimo rendimento após a otimização. Em nosso conhecimento, este é o primeiro método a empregar Ni(II) para síntese de estirenos substituídos por reação de acoplamento de Suzuki. A metodologia foi utilizada para a obtenção de derivados funcionalizados do estireno, usando-se ácidos arilborônicos substituídos, e mostrou-se eficaz quando da utilização de substituintes retiradores de elétrons nos ácidos arilborônicos, atingindo rendimentos superiores aos obtidos com paládio (F, CF3). O método não foi eficiente para obtenção de estirenos substituídos com grupos doadores de elétrons, resultando geralmente em grandes quantidades do subproduto de desboronação. O estudo dos efeitos eletrônicos (correlação de Hammett) para este sistema mostrou que ácidos arilborônicos com substituintes doadores de elétrons são mais reativos. Evidências cinéticas sugerem que a transmetalação possa ser a etapa limitante da velocidade da reação de Suzuki do brometo de vinila catalisada por NiCl2(PPh3)2. Embora o acoplamento de Suzuki do (E)-bromoestilbeno com ácido fenilborônico seja mais lento e mais sensível aos efeitos estéreos quando se comparam os catalisadores de níquel com os de paládio, o níquel apresenta a vantagem de ser um metal mais acessível e barato. Finalmente, um reagente de Grignard foi empregado na tentativa de efetuar o acoplamento do (E)-bromoestilbeno pela reação de Kumada-Corriu catalisada por níquel, mas testes preliminares não conduziram a resultados satisfatórios. / This work describes a study on the Suzuki cross-coupling reaction between vinyl bromide and (E)-bromo stilbene and arylboronic acids using nickel complexes. An efficient catalytic system for styrene synthesis in excellent yield was developed using the Suzuki cross-coupling reaction catalyzed by NiCl2(PPh3)2. As far as we are concerned this is the first method to use Ni(II) to synthesize substituted styrenes by the Suzuki reaction. The methodology developed was employed to obtain functionalized derivatives of styrene from substituted arylboronic acids and it was efficient for electron withdrawing groups on the arylboronic acids. Nevertheless this method was not efficient when electron donating groups where used and it resulted in great quantities of the deboronation product. The study on the electronic effects (Hammett correlation) for this system showed that arylboronic acids with electron donating groups are more reactive. Kinetic evidences suggest that the transmetalation step could be the limiting step of the Suzuki cross-coupling reaction between vinyl bromide and arylboronic acids catalyzed by NiCl2(PPh3)2. Despite the fact that Suzuki cross-coupling reaction between (E)-bromo stilbene and arylboronic acids is slower and more sensitive to steric hindrance when comparing nickel catalysts with palladium ones, nickel has the advantage of being a cheaper and more accessible metal. Finally a Grignard reagent was employed in attempt to perform the coupling of (E)-bromo stilbene by the Kumada-Corriu cross-coupling reaction catalyzed by nickel, but preliminary tests have not led to satisfactory results.

<p>Abstract</p><p>The purpose of my study is to compare Sten Rydhs wiew of learning disabilities in mathematics and his education with current literature and research. I want to explore whether the education of “Mattesmedjan”*, influenced by the Suzuki method, can be the solution for the students with maths problems. “Mattesmedjan” is a privately-owned school of maths. Some literature studies preceded the interview with “Mattesmedjan`s” founder, Sten Rydh, and this interview is the basis for my investigation. The interview was recorded on tape, then written out and finally the interview answers have been compiled.</p><p>There are various definitions and concepts of what learning disabilities in mathematics are about, for example dyscalculia and pseudo-dyscalculia. The scientists do not agree on the causes, but a vast majority of the problems seem to have psychological factors as the basis.</p><p>To help students with learning disabilities in mathematics, the teacher should have profound knowledge not only in his/her subject, but also in how students learn. The teacher should adapt his/her teaching to the students needs, examine what the student already knows and then build on this. A laboratory approach to the subject with concrete examples and discussions makes mathematics easier for the student. Not only the learning methods but also the environmental impact are of great importance to the students mathematics development.</p><p>*“Mattesmedjan” may be freely translated as workshop for mathematics.</p> / <p>Sammanfattning</p><p>Syftet med min undersökning är att jämföra Sten Rydhs åsikter om matematiksvårigheter och hans pedagogik med aktuell litteratur och forskning. Jag vill på så sätt undersöka om Mattesmedjans pedagogik, som influerats av Suzuki-metoden, kan vara lösningen för elever med problem. Mattesmedjan är en matteskola som drivs privat. Litteraturstudier föregick den intervju med Mattesmedjans grundare, Sten Rydh, som ligger till grund för undersökningen. Intervjun spelades in på band, skrevs sedan ut och intervjusvaren har sedan sammanställts.</p><p>Det finns olika definitioner om vad matematiksvårigheter är och det förekommer många begrepp ex dyskalkyli och pseudo- dyskalkyli. Forskarna är inte eniga om orsakerna men övervägande delen problem tenderar ha psykologiska faktorer som grund.</p><p>För att hjälpa elever med matematiksvårigheter bör läraren ha goda ämneskunskaper och insikter i hur elever lär in. Pedagogen bör anpassa undervisningen efter elevens behov, undersöka vad eleven redan kan och bygga vidare på detta. Ett laborativt arbetssätt där man konkretiserar och pratar matematik underlättar för eleven. Det är inte bara inlärningsmetoden som har stor betydelse för elevens fortsatta utveckling, även miljön inverkar.</p><p>Nyckelord: matematiksvårigheter, Mattesmedjan, pedagogik, Suzuki-metoden.</p>

Thesis (M.Phil.) - University of Queensland, 2006. / Includes bibliography.

Abstract The purpose of my study is to compare Sten Rydhs wiew of learning disabilities in mathematics and his education with current literature and research. I want to explore whether the education of “Mattesmedjan”*, influenced by the Suzuki method, can be the solution for the students with maths problems. “Mattesmedjan” is a privately-owned school of maths. Some literature studies preceded the interview with “Mattesmedjan`s” founder, Sten Rydh, and this interview is the basis for my investigation. The interview was recorded on tape, then written out and finally the interview answers have been compiled. There are various definitions and concepts of what learning disabilities in mathematics are about, for example dyscalculia and pseudo-dyscalculia. The scientists do not agree on the causes, but a vast majority of the problems seem to have psychological factors as the basis. To help students with learning disabilities in mathematics, the teacher should have profound knowledge not only in his/her subject, but also in how students learn. The teacher should adapt his/her teaching to the students needs, examine what the student already knows and then build on this. A laboratory approach to the subject with concrete examples and discussions makes mathematics easier for the student. Not only the learning methods but also the environmental impact are of great importance to the students mathematics development. *“Mattesmedjan” may be freely translated as workshop for mathematics. / Sammanfattning Syftet med min undersökning är att jämföra Sten Rydhs åsikter om matematiksvårigheter och hans pedagogik med aktuell litteratur och forskning. Jag vill på så sätt undersöka om Mattesmedjans pedagogik, som influerats av Suzuki-metoden, kan vara lösningen för elever med problem. Mattesmedjan är en matteskola som drivs privat. Litteraturstudier föregick den intervju med Mattesmedjans grundare, Sten Rydh, som ligger till grund för undersökningen. Intervjun spelades in på band, skrevs sedan ut och intervjusvaren har sedan sammanställts. Det finns olika definitioner om vad matematiksvårigheter är och det förekommer många begrepp ex dyskalkyli och pseudo- dyskalkyli. Forskarna är inte eniga om orsakerna men övervägande delen problem tenderar ha psykologiska faktorer som grund. För att hjälpa elever med matematiksvårigheter bör läraren ha goda ämneskunskaper och insikter i hur elever lär in. Pedagogen bör anpassa undervisningen efter elevens behov, undersöka vad eleven redan kan och bygga vidare på detta. Ett laborativt arbetssätt där man konkretiserar och pratar matematik underlättar för eleven. Det är inte bara inlärningsmetoden som har stor betydelse för elevens fortsatta utveckling, även miljön inverkar. Nyckelord: matematiksvårigheter, Mattesmedjan, pedagogik, Suzuki-metoden.