A Ring Contraction Strategy toward a Diastereoselective Total Synthesis of (+)-Bakkenolide A

A diastereoselective route to (+)-bakkenolide A is presented from the readily available optically active Wieland-Miescher ketone. This novel synthesis of this sesquiterpene lactone features the following as key stereoselective transformations: (i) the ring contraction reaction of a octalone mediated by thallium(III) nitrate (TTN); (ii) a hydrogenation to create the cis-fused junction; and (iii) the formation of the C7 quaternary center through an enolate intermediate. Furthermore, during this work, the absolute configuration of a trinorsesquiterpene isolated from Senecio Humillimus was assigned.

Iodine(III)-promoted ring expansion of 1-vinylcycloalkanol derivatives: A metal-free approach toward seven-membered rings

A versatile and metal-free approach for the synthesis of molecules bearing seven- and eight-membered rings is described. The strategy is based on the ring expansion of 1-vinylcycloalkanols (or the corresponding silyl or methyl ether) mediated by the hypervalent iodine reagent HTIB (Phl(OH)OTs). The reaction condition can be easily adjusted to give seven-membered rings bearing different functional groups. A route to medium-ring lactones was also developed.

Ring Contraction of 1,2-Dihydronaphthalenes Promoted by Thallium(III) in Acetonitrile: A Diastereoselective Approach to Indanes

trans-1,3-Disubstituted indanes are conveniently accessed by a stereoselective ring contraction of 1,2-dihydronaphthalenes upon treatment with thallium(III) nitrate (TTN) in acetonitrile. Under these conditions, the oxidative rearrangement of either di- or trisubstituted double bonds is possible.

A Diastereoselective Total Synthesis of trans-Trikentrin A: A Ring Contraction Approach

A new route to obtain the polyalkylated indole (+/-)-trans-trikentrin A was developed. The synthesis of this natural alkaloid features a thallium(III)mediated ring contraction reaction to obtain the trans-1,3-disubstituted five-membered ring in a diastereoselective manner. Thallium(III) is chemoselective in this rearrangement, reacting with the olefin without oxidation of the indole moiety. Other key transformations are the Bartoli`s reaction to construct the heterocyclic ring and a Heck coupling to add the carbons atom that will originate the nonaromatic cycle.

Thomas-Fermi ground state of dipolar fermions in a circular storage ring

Recent developments in the field of ultracold gases has led to the production of degenerate samples of polar molecules. These have large static electric-dipole moments, which in turn causes the molecules to interact strongly. We investigate the interaction of polar particles in waveguide geometries subject to an applied polarizing field. For circular waveguides, tilting the direction of the polarizing field creates a periodic inhomogeneity of the interparticle interaction. We explore the consequences of geometry and interaction for stability of the ground state within the Thomas-Fermi model. Certain combinations of tilt angles and interaction strengths are found to preclude the existence of a stable Thomas-Fermi ground state. The system is shown to exhibit different behavior for quasi-one-dimensional and three-dimensional trapping geometries.

Opening the Windows of the Church to the World: The Creation of Nostra Aetate and Its Impact on the Christian-Jewish relationship

It is important to assert that this study is not a work to inflict guilt on the Catholics or Catholicism for their silence and indifference during the Holocaust. Instead, this study is about the process of moving on from the Catholic Church's past to where the Jewish community's theological existence was finally recognized and the Jewish people were no longer seen as the Others who killed Christ. This was, achieved through a church declaration titled Nostra Aetate (In Our Time). This study records the journey traversed by this declaration, the insurmountable odds it faced in its creation until its promulgation and the impact it has on the Jewish-Christian relationship.

Synthesis of 2-oxo-16-(3', 4'-methylenedioxyphenyl)-trans-15-hexadecene

This work presents the progress made towards synthesizing 2-oxo-16-(3', 4'methylenedioxyphenyl)-trans-15-hexadecene, an antimycobacterial compound that was originally isolated from the leaves of Piper Sanctum. The hydrocarbon chain of the molecule was synthesized first by opening a 15-pentadecanolactone ring by means of HI, and performing an E2 elimination reaction on the molecule followed by an organolithium reaction with CH3Li. Hexadec-15-en-2-one that was afforded this way was later reacted with 5-bromobenzo[d][1,3]dioxole following the appropriate Heck reaction protocol that allows for the formation of a palladium catalyzed carbon-carbon bond. The modes of action of 2-oxo-16-(3', 4'-methylenedioxyphenyl)-trans-15hexadecene are comparable to the ones of rifampicin, a marketable drug that has been successfully used in the treatment of tuberculosis in the past. Additionally, this compound can serve as an intermediate towards the synthesis of 2-oxo-16-(3', 4' methylenedioxyphenyl)-hexadecane and 2-oxo-14-(3', 4' -methylenedioxyphenyl) tetradecane, both strong inhibitors of the growth of Mycobacterium tuberculosis. Lastly, due to Multi-Drug Resistant tuberculosis, there has been an increasing need to find alternative cures for tuberculosis. Therefore, the work on 2-qxo-16-(3', 4'methylenedioxyphenyl)-trans-15-hexadecene is not only chemically interesting but it is also biologically important.

Colby News

Modeling Clean Energy A New Home Sweet Home Opening a Dialogue Walking in Someone Else's Shoes Delayed Reaction, Strong Occupation New Affiliation with Columbia Same Place, Different Mission Giving Marriage a New Ring TwitterFEED Microcosm of a Small World

November 2000: Seeing is Believing, Library Changes Since Opening of Dacus

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How the full opening of the capital account to highly liquid financial markets led Latin America to two and a half cycles of ‘mania, panic and crash’

Latin America has recently experienced three cycles of capital inflows, the first two ending in major financial crises. The first took place between 1973 and the 1982 ‘debt-crisis’. The second took place between the 1989 ‘Brady bonds’ agreement (and the beginning of the economic reforms and financial liberalisation that followed) and the Argentinian 2001/2002 crisis, and ended up with four major crises (as well as the 1997 one in East Asia) — Mexico (1994), Brazil (1999), and two in Argentina (1995 and 2001/2). Finally, the third inflow-cycle began in 2003 as soon as international financial markets felt reassured by the surprisingly neo-liberal orientation of President Lula’s government; this cycle intensified in 2004 with the beginning of a (purely speculative) commodity price-boom, and actually strengthened after a brief interlude following the 2008 global financial crash — and at the time of writing (mid-2011) this cycle is still unfolding, although already showing considerable signs of distress. The main aim of this paper is to analyse the financial crises resulting from this second cycle (both in LA and in East Asia) from the perspective of Keynesian/ Minskyian/ Kindlebergian financial economics. I will attempt to show that no matter how diversely these newly financially liberalised Developing Countries tried to deal with the absorption problem created by the subsequent surges of inflow (and they did follow different routes), they invariably ended up in a major crisis. As a result (and despite the insistence of mainstream analysis), these financial crises took place mostly due to factors that were intrinsic (or inherent) to the workings of over-liquid and under-regulated financial markets — and as such, they were both fully deserved and fairly predictable. Furthermore, these crises point not just to major market failures, but to a systemic market failure: evidence suggests that these crises were the spontaneous outcome of actions by utility-maximising agents, freely operating in friendly (‘light-touch’) regulated, over-liquid financial markets. That is, these crises are clear examples that financial markets can be driven by buyers who take little notice of underlying values — i.e., by investors who have incentives to interpret information in a biased fashion in a systematic way. Thus, ‘fat tails’ also occurred because under these circumstances there is a high likelihood of self-made disastrous events. In other words, markets are not always right — indeed, in the case of financial markets they can be seriously wrong as a whole. Also, as the recent collapse of ‘MF Global’ indicates, the capacity of ‘utility-maximising’ agents operating in (excessively) ‘friendly-regulated’ and over-liquid financial market to learn from previous mistakes seems rather limited.

How the full opening of the capital account to highly liquid financial markets led Latin America to two and a half cycles of ‘mania, panic and crash’

Latin America has recently experienced three cycles of capital inflows, the first two ending in major financial crises. The first took place between 1973 and the 1982 ‘debt-crisis’. The second took place between the 1989 ‘Brady bonds’ agreement (and the beginning of the economic reforms and financial liberalisation that followed) and the Argentinian 2001/2002 crisis, and ended up with four major crises (as well as the 1997 one in East Asia) — Mexico (1994), Brazil (1999), and two in Argentina (1995 and 2001/2). Finally, the third inflow-cycle began in 2003 as soon as international financial markets felt reassured by the surprisingly neo-liberal orientation of President Lula’s government; this cycle intensified in 2004 with the beginning of a (purely speculative) commodity price-boom, and actually strengthened after a brief interlude following the 2008 global financial crash — and at the time of writing (mid-2011) this cycle is still unfolding, although already showing considerable signs of distress. The main aim of this paper is to analyse the financial crises resulting from this second cycle (both in LA and in East Asia) from the perspective of Keynesian/ Minskyian/ Kindlebergian financial economics. I will attempt to show that no matter how diversely these newly financially liberalised Developing Countries tried to deal with the absorption problem created by the subsequent surges of inflow (and they did follow different routes), they invariably ended up in a major crisis. As a result (and despite the insistence of mainstream analysis), these financial crises took place mostly due to factors that were intrinsic (or inherent) to the workings of over-liquid and under-regulated financial markets — and as such, they were both fully deserved and fairly predictable. Furthermore, these crises point not just to major market failures, but to a systemic market failure: evidence suggests that these crises were the spontaneous outcome of actions by utility-maximising agents, freely operating in friendly (light-touched) regulated, over-liquid financial markets. That is, these crises are clear examples that financial markets can be driven by buyers who take little notice of underlying values — investors have incentives to interpret information in a biased fashion in a systematic way. ‘Fat tails’ also occurred because under these circumstances there is a high likelihood of self-made disastrous events. In other words, markets are not always right — indeed, in the case of financial markets they can be seriously wrong as a whole. Also, as the recent collapse of ‘MF Global’ indicates, the capacity of ‘utility-maximising’ agents operating in unregulated and over-liquid financial market to learn from previous mistakes seems rather limited.

Opening ILT blackbox: Exploring recognition-based leadership perceptions with conjoint analysis

Although research on Implicit Leadership Theories (ILT) has put great effort on determining what attributes define a leader prototype, little attention has been given to understanding the relative importance of each of these attributes in the categorization process by followers. Knowing that recognition-based leadership perceptions are the result of the match between followers’ ILTs and the perceived attributes in their actual leaders, understanding how specific prototypical leader attributes impact this impression formation process is particularly relevant. In this study, we draw upon socio-cognitive theories to explore how followers cognitively process the information about a leader’s attributes. By using Conjoint Analysis (CA), a technique that allows us to measure an individual’s trade-offs when making choices about multi-attributed options, we conducted a series of 4 studies with a total of 879 participants. Our results demonstrate that attributes’ importance for individuals’ leadership perceptions formation is rather heterogeneous, and that some attributes can enhance or spoil the importance of other prototypical attributes. Finally, by manipulating the leadership domain, we show that the weighting pattern of attributes is context dependent, as suggested by the connectionist approach to leadership categorization. Our findings also demonstrate that Conjoint Analysis can be a valuable tool for ILT research.

Chemical and microbiological changes and aerobic stability of marandu grass silages after silo opening

Esta pesquisa foi realizada com os objetivos de caracterizar a microbiologia e avaliar a estabilidade aeróbia de silagens de capim-marandu contendo polpa cítrica peletizada (PCP). A forragem colhida foi submetida aos seguintes tratamentos: silagem de capim-marandu; silagem de capim-marandu + 5% PCP e silagem do capim-marandu + 10% de PCP com base na matéria natural. As alterações químicas e microbiológicas foram feitas aos 0, 2, 4 e 6 dias após a abertura dos silos (tambores de metal com 80 cm de altura e 50 cm de diâmetro). Na avaliação da estabilidade aeróbia por meio da alteração da temperatura, 3 kg de silagem foram colocados em caixas de isopor, que foram armazenadas em câmara climática. Nos dois ensaios realizados, utilizou-se delineamento inteiramente ao acaso com cinco repetições, em esquema de parcelas subdivididas, de modo que os níveis de PCP na silagem corresponderam às parcelas e o tempo, às subparcelas. As silagens sem polpa apresentaram desenvolvimento de bacilos e enterobactérias e aumento do pH no decorrer do desabastecimento dos silos. A presença de leveduras foi detectada nas silagens contendo o aditivo e aumentou do primeiro ao sexto dia de aeração. A digestibilidade in vitro da matéria seca (DIVMS) reduziu com o aumento dos tempos de aeração. A temperatura nas silagens com 10% de PCP aumentou durante a aerobiose. Com a abertura dos silos, as silagens apresentaram-se instáveis, seja pelo desenvolvimento de bactérias seja pelo desenvolvimento de leveduras, o que reduziu seu valor nutritivo.

Extração e Representação de Conhecimento de Séries Temporais de Demanda de Energia Elétrica Usando TSKR

The opening of the Brazilian market of electricity and competitiveness between companies in the energy sector make the search for useful information and tools that will assist in decision making activities, increase by the concessionaires. An important source of knowledge for these utilities is the time series of energy demand. The identification of behavior patterns and description of events become important for the planning execution, seeking improvements in service quality and financial benefits. This dissertation presents a methodology based on mining and representation tools of time series, in order to extract knowledge that relate series of electricity demand in various substations connected of a electric utility. The method exploits the relationship of duration, coincidence and partial order of events in multi-dimensionals time series. To represent the knowledge is used the language proposed by Mörchen (2005) called Time Series Knowledge Representation (TSKR). We conducted a case study using time series of energy demand of 8 substations interconnected by a ring system, which feeds the metropolitan area of Goiânia-GO, provided by CELG (Companhia Energética de Goiás), responsible for the service of power distribution in the state of Goiás (Brazil). Using the proposed methodology were extracted three levels of knowledge that describe the behavior of the system studied, representing clearly the system dynamics, becoming a tool to assist planning activities