Z-selective olefin metathesis using chelating ruthenium alkylidene catalysts

Publications about olefin metathesis will generally discuss how the discovery and development of well-defined catalysts to carry out this unique transformation have revolutionized many fields, from natural product and materials chemistry, to green chemistry and biology. However, until recently, an entire manifestation of this methodology had been inaccessible. Except for a few select examples, metathesis catalysts favor the thermodynamic trans- or E-olefin products in cross metathesis (CM), macrocyclic ring closing metathesis (mRCM), ring opening metathesis polymerization (ROMP), and many other types of reactions. Judicious choice of substrates had allowed for the direct synthesis of cis- or Z-olefins or species that could be converted upon further reaction, however the catalyst controlled synthesis of Z-olefins was not possible until very recently.

Research into the structure and stability of metallacyclobutane intermediates has led to the proposal of models to impart Z-selectivity in metathesis reactions. Having the ability to influence the orientation of metallacyclobutane substituents to cause productive formation of Z- double bonds using steric and electronic effects was highly desired. The first successful realization of this concept was by Schrock and Hoveyda et al. who synthesized monoaryloxide pyrolidine (MAP) complexes of tungsten and molybdenum that promoted Z-selective CM. The Z-selectivity of these catalysts was attributed to the difference in the size of the two axial ligands. This size difference influences the orientation of the substituents on the forming/incipient metallacyclobutane intermediate to a cis-geometry and leads to productive formation of Z-olefins. These catalysts have shown great utility in the synthesis of complicated natural product precursors and stereoregular polymers. More recently, ruthenium catalysts capable of promoting Z-selective metathesis have been reported by our group and others. This thesis will discuss the development of ruthenium-based NHC chelated Z-selective catalysts, studies probing their unique metathesis mechanism, and synthetic applications that have been investigated thus far.

Chapter 1 will focus on studies into the stability of NHC chelated complexes and the synthesis of new and improved stable chelating architectures. Chapter 2 will discuss applications of the highly active and Z-selective developed in Chapter 1, including the formation of lepidopteran female sex pheromones using olefin cross metathesis and highly Z- and highly E-macrocycles using macrocyclic ring closing metathesis and Z-selective ethenolysis. Chapter 3 will explore studies into the unique mechanism of olefin metathesis reactions catalyzed by these NHC chelated, highly Z-selective catalysts, explaining observed trends by investigating the stability of relevant, substituted metallacyclobutane intermediates.

利用原子芯片上Z形磁阱囚禁中性^87Rb原子

利用解析和数值方法计算了Z形磁阱的囚禁势,发现当囚禁中心和芯片表面距离较远时（该距离和Z形线中部导线的一半长度相差不超过一个量级）,势阱的深度不能近似表示成偏置磁场By对应的能量,而要减去囚禁中心的势能高度;而增加By进行磁阱压缩到一定值时,势阱深度反而会下降.此外介绍了原子芯片的制作方法,以及利用原子芯片上Z形磁阱囚禁中性87Rb原子的实验装置和实验过程.最终有2×10^6个^87Rb原子被转移到Z形磁阱中.

A biologically active peptide in the skin of lampreys (Eudontomyzon danfordi vladykovi). [Translation from: Z.Naturforsch. (B), 26(10), 1021-1023, 1971. ]

In recent years interest in the production and description of kinin-type substances has been greatly intensified. So, for example, bradykinin, phyllokinin, physalaemin, ranatensin and caerulein could be extracted from the skin of amphibians as well as. eledoisin out of the salivary glands of Eledon moschata. An examination of lampreys seemed to us particularly profitable in the search for the incidence of further kinins. Ammocoetes of different sizes and also adults of both sexes of the species Eudontomyzon danfordi vladykovi were studied in this research. This species is found in many tributaries of the Danube. Skin extracts were tested on on isolated rat uterus, rat duodenum, guinea pig ileum and rabbit jejunum, further tests were done in order to determine a peptide character of the biologically active substance.

Determination of dissolved oxygen in water with leukoberbelin-blue I. A quick Winkler method. [Translation from: Z.analyt.Chem. 262 97-99, 1972.]

The reaction of Mn(II) with water-dissolved oxygen, to a higher manganese hydroxide in an alkaline medium, as with the longstanding classic Winkler method, is the first step in the method described here. The assumption for faultless results by the conventional and modified Winkler method is clean water, which contains no organic substances by Mn(III) or Mn(IV). In many cases, however, eg. in river and lake-water tests, it can be seen with the naked eye that after some time the originally brown-coloured precipitate of manganese hydroxide becomes more and more colourless. Oxygen content was analysed in the water samples and evaluated by raising the amount of the leuko-base and giving the corresponding dilution of the colouring matter solution formed still higher oxygen contents can be measured.

Studies on heterotrophic nitrification in a lake. [Translation from: Z.allg.Mikrobiol. 12 567-574, 1973. ]

In a lake the nitrogen compounds are liable to regular cycling in which nitrate is reduced and ammonium oxidised. As a nitrate maximum is regularly established in the upper part of the hypolimnion of a stratified summer lake, the authors have dealt in particular with the oxidising side of the nitrogen cycle. Described here are partial results of the nitrification in Plusssee. The Plusssee was chosen, since it is almost entirely without inflows, and, lying in a wooded basin, is well protected from the wind, and therefore stably stratified. In order to determine the number of autotrophic nitrificants the distribution of the Nitrosomonas and Nitrobacter spores in the lake were analysed. From the estimates on the determination of spore numbers of the heterotrophic nitrificants, 14 species in the pure culture were isolated and examined from morphological, biochemical and taxonomic viewpoints.

Physiology of nitrate reduction in Pseudomonas aeruginosa. [Translation from: Z.allg.Mikrobiol. 13, 83-94, 1973.]

Pseudomonas aeruginosa has for some time been known as a denitrifier. Pseudomonas aeruginosa was chosen for further studies, because P. aeruginosa occurs abundantly in Plusssee and moreover there are contradictory assertions on the gas products of denitrification by this bacteria. In experimental research the pattern of growth and gas production of Pseudomonas aeruginosa on nutrient broth was studied.

Experimental research on the development of Ceratium hirundinella O.F.Muller [Translation from: Z.Bot. 14, 337-371, 1922]

The most important aim of this study lay in filling in the great gap in our knowledge of the processes of germination in the Ceratium cyst and the early developmental stages in the standing stock of Ceratium hirundinella. contained rich cysts, we now succeeded extraordinarily well in pursuing the consistent development of Ceratium from the cyst to the completed cell. A series of experiments were carried out on the cysts and the juvenile stages of Ceratium, which showed very interesting results. The author presents in a general descriptive part the normal processes of germination in Ceratium cysts and the development of the juvenile stages in order to show in an experimental part the changes in form of C. hirundinella under the influence of temperature, light and varying salinities.

A Z-scan model for optical nonlinear nanometric films

The Z-scan technique is useful for measuring the nonlinear refractive index of thin films. In conventional Z-scan theories, two effects are often ignored, namely the losses due to the internal multi-interference and the nonlinear absorption inside the sample. Therefore, the theories are restricted to relatively thick films. For films thinner than about 100 nm, the two effects become significant, and thus cannot be ignored. In the present work, we present a Z-scan theory that takes both effects into account. The proposed model calculation is suitable for optical nonlinear films of nanometric thickness. With numerical simulations, we demonstrate dramatic deviations from the conventional Z-scan calculations.

Estudo do escalonamento de volume finito na transição de fase do grupo de calibre Z(2) na rede

Neste trabalho estudamos a dependência com o tamanho do sistema dos observáveis relacionados com a transição de fase de 1 ordem do rupo de calibre Z(2) em 4 dimensões. Foram realizadas simulações de Monte Carlo numa rede cúbica para diferentes valores da aresta, utilizando o método do Banho Térmico para sortear os elementos do grupo na rede.

Procura do bóson de Higgs a partir da fusão de bósons vetoriais no Experimento CMS

O presente trabalho tem por finalidade determinar a luminosidade necessária para se impor um limite para exclusão e a signifucância para evidência e descoberta para um bóson de Higgs de mH = 200 GeV no canal qqH → ZZ → 4. Também, apresenta-se uma crítica a qualidade da relação sinal/fundo em eventos de fusão de bósons vetoriais conhecida da literatura atual.

New chiral E- and Z-isomers of the 1R,4R-2-arylidene-p-menthane-3-ones in induced cholesteric and ferroelectric liquid crystals

A novel pair of the E- and Z-isomeric 1R,4R-2-(4-heptyloxyphenyl)-benzylidene-p-menthan-3-ones has been prepared and the influence of distinctions in their molecular geometry on macroscopic properties of liquid crystal systems with the induced supra-molecular helical structure has been studied. The significantly lower helical twisting power of the chiral Z-isomer in comparison with that of E- one has been confirmed in the case of induced cholesteric systems based on 4-pentyl-4-cyanobiphenyl. The phase behavior and ferroelectric characteristics have been investigated for smectic-C* compositions based on the eutectic mixture of the homological 4-hexyloxyphenyl-4'-hexyloxy- and 4-hexyloxyphenyl-4'-octyloxybenzoates containing the novel isomeric chiral dopants. The spontaneous polarisation of the opposite signs induced by the isomeric chiral components has been revealed for the compositions studied. Distinctions in phase states, absolute values of the spontaneous polarization, smectic tilt angle and rotation viscosity of the systems obtained are discussed.