Anja Eleveld, Thomas Kampen, and Josien Arts
- Published in print:
- 2020
- Published Online:
- September 2020
- ISBN:
- 9781447340010
- eISBN:
- 9781447340164
- Item type:
- chapter
- Publisher:
- Policy Press
- DOI:
- 10.1332/policypress/9781447340010.003.0001
- Subject:
- Economics and Finance, Public and Welfare
In the last decades, rights to social assistance benefits have become more conditional. Governments in Europe, as in other welfare states, have sought to ‘activate’ their unemployed citizens by ...
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In the last decades, rights to social assistance benefits have become more conditional. Governments in Europe, as in other welfare states, have sought to ‘activate’ their unemployed citizens by requiring them to participate in mandatory work programmes. This chapter examines how liberal and communitarian thinkers have justified or rejected welfare-to-work (WTW) policies within social assistance systems and how these policies have been legitimised by key notions of inclusion, responsibilisation, employability and empowerment, which correspond with liberal and communitarian justifications of WTW. Drawing on critical socio-legal literature, the authors question these justifications and clarify their decision to explore WTW from a threefold normative perspective that takes into account: 1) power relations and human social rights (the legal perspective); 2) lived experiences within WTW relationships, including endemic power asymmetries and perceptions of justice (the sociological perspective); and 3) the republican theory of non-domination (the philosophical perspective). The last part of this chapter introduces the chapters of this book.Less
In the last decades, rights to social assistance benefits have become more conditional. Governments in Europe, as in other welfare states, have sought to ‘activate’ their unemployed citizens by requiring them to participate in mandatory work programmes. This chapter examines how liberal and communitarian thinkers have justified or rejected welfare-to-work (WTW) policies within social assistance systems and how these policies have been legitimised by key notions of inclusion, responsibilisation, employability and empowerment, which correspond with liberal and communitarian justifications of WTW. Drawing on critical socio-legal literature, the authors question these justifications and clarify their decision to explore WTW from a threefold normative perspective that takes into account: 1) power relations and human social rights (the legal perspective); 2) lived experiences within WTW relationships, including endemic power asymmetries and perceptions of justice (the sociological perspective); and 3) the republican theory of non-domination (the philosophical perspective). The last part of this chapter introduces the chapters of this book.
Anja Eleveld, Thomas Kampen, and Josien Arts (eds)
- Published in print:
- 2020
- Published Online:
- September 2020
- ISBN:
- 9781447340010
- eISBN:
- 9781447340164
- Item type:
- book
- Publisher:
- Policy Press
- DOI:
- 10.1332/policypress/9781447340010.001.0001
- Subject:
- Economics and Finance, Public and Welfare
With welfare to work programmes under intense scrutiny, this book reviews a wide range of existing and future policies across Europe.
Seventeen contributors provide case studies and legal, ...
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With welfare to work programmes under intense scrutiny, this book reviews a wide range of existing and future policies across Europe.
Seventeen contributors provide case studies and legal, sociological and philosophical perspectives from around the continent, building a rich picture of welfare to work policies and their impact. They show how many schemes do not adequately address social rights and lived experiences, and consider alternatives based on theories of non-domination.
For anyone interested in the justice of welfare to work, this book is an important step along the path towards more fair and adequate legislation.Less
With welfare to work programmes under intense scrutiny, this book reviews a wide range of existing and future policies across Europe.
Seventeen contributors provide case studies and legal, sociological and philosophical perspectives from around the continent, building a rich picture of welfare to work policies and their impact. They show how many schemes do not adequately address social rights and lived experiences, and consider alternatives based on theories of non-domination.
For anyone interested in the justice of welfare to work, this book is an important step along the path towards more fair and adequate legislation.
Katharina Zimmermann
- Published in print:
- 2019
- Published Online:
- May 2020
- ISBN:
- 9781447346517
- eISBN:
- 9781447346555
- Item type:
- book
- Publisher:
- Policy Press
- DOI:
- 10.1332/policypress/9781447346517.001.0001
- Subject:
- Political Science, Public Policy
In the context of an ‘activation turn’ in many European welfare states, the local level gained increasing relevance in the last decades and brought local social policies and national employment ...
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In the context of an ‘activation turn’ in many European welfare states, the local level gained increasing relevance in the last decades and brought local social policies and national employment policies more closely together. At the same time, at the European level the European Social Fund (ESF) made a career from an unconditional simple financing instrument towards a complex governance tool; meant to back up European social and employment policies in close combination with tools such as reporting or benchmarking. Greater coordination of domestic policies in social and employment policies, where the EU had no regulative competences, was sought to be achieved via ‘bypass strategies’ which directly focused on the subnational implementation systems of the member states. Against the backdrop of these scenarios, the book is interested in the actual role of the ESF in local activation policies. It wants to know how local social and employment policy fields react to the ESF, what shapes their reactions, and what the effects of these reactions are in terms of change in local policy fields. By drawing on both sociologists’ and political scientists’ literature, the book develops a unique perspective on the role of supranational money at the local level. By comparing comprehensive qualitative data from 18 local case studies in six European countries (Sweden, France, Poland, UK, Italy, and Germany) and deploying an innovative mixed-method approach, the book provides rich insights into a field where so far comparative qualitative research is missing.Less
In the context of an ‘activation turn’ in many European welfare states, the local level gained increasing relevance in the last decades and brought local social policies and national employment policies more closely together. At the same time, at the European level the European Social Fund (ESF) made a career from an unconditional simple financing instrument towards a complex governance tool; meant to back up European social and employment policies in close combination with tools such as reporting or benchmarking. Greater coordination of domestic policies in social and employment policies, where the EU had no regulative competences, was sought to be achieved via ‘bypass strategies’ which directly focused on the subnational implementation systems of the member states. Against the backdrop of these scenarios, the book is interested in the actual role of the ESF in local activation policies. It wants to know how local social and employment policy fields react to the ESF, what shapes their reactions, and what the effects of these reactions are in terms of change in local policy fields. By drawing on both sociologists’ and political scientists’ literature, the book develops a unique perspective on the role of supranational money at the local level. By comparing comprehensive qualitative data from 18 local case studies in six European countries (Sweden, France, Poland, UK, Italy, and Germany) and deploying an innovative mixed-method approach, the book provides rich insights into a field where so far comparative qualitative research is missing.
Elise Dermine
- Published in print:
- 2020
- Published Online:
- September 2020
- ISBN:
- 9781447340010
- eISBN:
- 9781447340164
- Item type:
- chapter
- Publisher:
- Policy Press
- DOI:
- 10.1332/policypress/9781447340010.003.0003
- Subject:
- Economics and Finance, Public and Welfare
The promoters of welfare-to-work programmes sometimes state that these are based on the will to ‘better realise’ the right to work of their recipients. This chapter questions this assumption and ...
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The promoters of welfare-to-work programmes sometimes state that these are based on the will to ‘better realise’ the right to work of their recipients. This chapter questions this assumption and examines whether and under which conditions, those programmes could eventually find their foundation on the fundamental right to work proclaimed in international human rights texts. It demonstrates from an analysis of the international pacts, their preparatory texts and the case law that welfare-to-work measures can only be considered as aimed at realising the right to work if they are likely to improve the chances of their recipients to later find a freely chosen, paid and productive job in the labour market. It shows that this open and abstract condition excludes a large part of welfare-to-work measures from a human rights-based justification for the type of work they value or the way they are implemented.Less
The promoters of welfare-to-work programmes sometimes state that these are based on the will to ‘better realise’ the right to work of their recipients. This chapter questions this assumption and examines whether and under which conditions, those programmes could eventually find their foundation on the fundamental right to work proclaimed in international human rights texts. It demonstrates from an analysis of the international pacts, their preparatory texts and the case law that welfare-to-work measures can only be considered as aimed at realising the right to work if they are likely to improve the chances of their recipients to later find a freely chosen, paid and productive job in the labour market. It shows that this open and abstract condition excludes a large part of welfare-to-work measures from a human rights-based justification for the type of work they value or the way they are implemented.
Mathias H. Nielsen, Sophie Danneris, and Niklas A. Andersen
- Published in print:
- 2020
- Published Online:
- September 2020
- ISBN:
- 9781447340010
- eISBN:
- 9781447340164
- Item type:
- chapter
- Publisher:
- Policy Press
- DOI:
- 10.1332/policypress/9781447340010.003.0008
- Subject:
- Economics and Finance, Public and Welfare
The chapter explores how Danish WTW policies have recently been implemented and extended while to a large degree avoiding the hazards of public justification. The chapter investigates three cases, ...
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The chapter explores how Danish WTW policies have recently been implemented and extended while to a large degree avoiding the hazards of public justification. The chapter investigates three cases, which exemplify three different ways to expand the scope of WTW polices, without them having to be publicly justified. The first case digs into classification processes where the work capability of Danish social assistance claimants is assessed. It shows how incremental changes of such processes have formed a system where more and more claimants are deemed capable of working – and therefore legitimate targets of harsher demands and sanctions. The second case explores how the political quest for evidence-based employment policies comes with an inherent bias: ‘Evidence’ is constructed in ways that clearly favour work first policies. The third case investigates how the municipal welfare offices’ autonomy to try out new and innovative activation programs, is currently being restructured by subtle changes that increase the incentives to take up activations programs that support WTW strategies.Less
The chapter explores how Danish WTW policies have recently been implemented and extended while to a large degree avoiding the hazards of public justification. The chapter investigates three cases, which exemplify three different ways to expand the scope of WTW polices, without them having to be publicly justified. The first case digs into classification processes where the work capability of Danish social assistance claimants is assessed. It shows how incremental changes of such processes have formed a system where more and more claimants are deemed capable of working – and therefore legitimate targets of harsher demands and sanctions. The second case explores how the political quest for evidence-based employment policies comes with an inherent bias: ‘Evidence’ is constructed in ways that clearly favour work first policies. The third case investigates how the municipal welfare offices’ autonomy to try out new and innovative activation programs, is currently being restructured by subtle changes that increase the incentives to take up activations programs that support WTW strategies.
Thomas Pfister
- Published in print:
- 2012
- Published Online:
- January 2013
- ISBN:
- 9780719083310
- eISBN:
- 9781781704653
- Item type:
- book
- Publisher:
- Manchester University Press
- DOI:
- 10.7228/manchester/9780719083310.001.0001
- Subject:
- Political Science, European Union
This book illuminates the links between the currently dominant transnational discourse on what constitutes ‘modern’ social policy and contemporary concepts and practices of citizenship. Throughout ...
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This book illuminates the links between the currently dominant transnational discourse on what constitutes ‘modern’ social policy and contemporary concepts and practices of citizenship. Throughout Europe, we are witnessing a large-scale reshuffling of welfare economies based on the guiding principles of ‘activation’ and an ‘activating welfare state’. Moreover, the European Union has become a major driving force behind this transformation. What are the consequences of this fundamental reorientation for citizenship? How does it relate to patterns of exclusion and inequality inherent in each historical citizenship formation? What exactly is the EU’s role in this context? The book examines how such a powerful conceptual debate intervenes in the conditions of political membership in terms of rights and duties, participation, and access to societal resources. The detailed qualitative study focuses on the European Employment Strategy (EES) – and in particular its gender equality dimension – as a central process where the activation agenda is constructed and equipped with meanings. It traces how this European debate has unfolded, how it has been received and translated into shifting practices of citizenship in three EU member states – Germany, the UK, and Hungary. The book provides instructive insights in how the activation discourse reshapes the conceptual foundations of citizenship. Despite their indirect and intellectual nature, these changes significantly intervene in the contested development and the exclusionary elements of citizenship.Less
This book illuminates the links between the currently dominant transnational discourse on what constitutes ‘modern’ social policy and contemporary concepts and practices of citizenship. Throughout Europe, we are witnessing a large-scale reshuffling of welfare economies based on the guiding principles of ‘activation’ and an ‘activating welfare state’. Moreover, the European Union has become a major driving force behind this transformation. What are the consequences of this fundamental reorientation for citizenship? How does it relate to patterns of exclusion and inequality inherent in each historical citizenship formation? What exactly is the EU’s role in this context? The book examines how such a powerful conceptual debate intervenes in the conditions of political membership in terms of rights and duties, participation, and access to societal resources. The detailed qualitative study focuses on the European Employment Strategy (EES) – and in particular its gender equality dimension – as a central process where the activation agenda is constructed and equipped with meanings. It traces how this European debate has unfolded, how it has been received and translated into shifting practices of citizenship in three EU member states – Germany, the UK, and Hungary. The book provides instructive insights in how the activation discourse reshapes the conceptual foundations of citizenship. Despite their indirect and intellectual nature, these changes significantly intervene in the contested development and the exclusionary elements of citizenship.
Sotiria Theodoropoulou (ed.)
- Published in print:
- 2018
- Published Online:
- September 2018
- ISBN:
- 9781447335863
- eISBN:
- 9781447335900
- Item type:
- book
- Publisher:
- Policy Press
- DOI:
- 10.1332/policypress/9781447335863.001.0001
- Subject:
- Sociology, Occupations, Professions, and Work
This book investigates whether, and if so how, the patterns of change of labour market policies in EU member states have altered since the emergence in 2010 of reinforced pressures on public spending ...
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This book investigates whether, and if so how, the patterns of change of labour market policies in EU member states have altered since the emergence in 2010 of reinforced pressures on public spending (‘fiscal austerity’). More specifically, the book explores, through national case studies, whether retrenchment or expansion have taken place; whether there has been a shift in the logic of activation policies; and how retrenchment and expansion of protection have been distributed across the well-protected and the less well-protected labour market populations. Looking at the big European picture, do we see a convergence or a divergence in labour market policy trends and outputs? Can we identify different patterns of change across member states? Last but not least, we ask whether there has been a divergence or convergence in labour market insecurity that can be associated with the ongoing policy changes and macroeconomic conditionsLess
This book investigates whether, and if so how, the patterns of change of labour market policies in EU member states have altered since the emergence in 2010 of reinforced pressures on public spending (‘fiscal austerity’). More specifically, the book explores, through national case studies, whether retrenchment or expansion have taken place; whether there has been a shift in the logic of activation policies; and how retrenchment and expansion of protection have been distributed across the well-protected and the less well-protected labour market populations. Looking at the big European picture, do we see a convergence or a divergence in labour market policy trends and outputs? Can we identify different patterns of change across member states? Last but not least, we ask whether there has been a divergence or convergence in labour market insecurity that can be associated with the ongoing policy changes and macroeconomic conditions
Yuk L. Yung and William B. DeMore
- Published in print:
- 1999
- Published Online:
- November 2020
- ISBN:
- 9780195105018
- eISBN:
- 9780197560990
- Item type:
- chapter
- Publisher:
- Oxford University Press
- DOI:
- 10.1093/oso/9780195105018.003.0007
- Subject:
- Earth Sciences and Geography, Atmospheric Sciences
Cosmology is a subject that borders on and sometimes merges with philosophy and religion. Since antiquity, the deep mysteries of the universe have intrigued mankind. ...
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Cosmology is a subject that borders on and sometimes merges with philosophy and religion. Since antiquity, the deep mysteries of the universe have intrigued mankind. Who are we? Where do we come from? What are we made of? Is the development of advanced intelligence capable of comprehending the grand design of the cosmos, the ultimate purpose of the universe? Is there life elsewhere in the universe? Is ours the only advanced intelligence or the most advanced intelligence in the universe? These questions have motivated great thinkers to pursue what Einstein called "the highest wisdom and the most radiant beauty." In the fourth century B.C., the essence of the cosmological question was formulated by the philosopher Chuang Tzu:… If there was a beginning, then there was a time before that beginning. And a time before the time which was before the time of that beginning. If there is existence, there must have been non-existence. And if there was a time when nothing existed, then there must be a time before that—when even nothing did not exist. Suddenly, when nothing came into existence, could one really say whether it belonged to the category of existence or of nonexistence? Even the very words I have just uttered, I cannot say whether they have really been uttered or not. There is nothing under the canopy of heaven greater than the tip of an autumn hair. A vast mountain is a small thing. Neither is there any age greater than that of a child cut off in infancy. P'eng Tsu [a Chinese Methuselah] himself died young. The universe and I came into being together; and I, and everything therein, are one. … Fortunately, our subject matter, solar system chemistry, is less esoteric than the questions asked by Chuang Tzu. A schematic diagram showing the principal pathways by which our solar system is formed is given in figure 4.1. The great triumphs of modern science have been summarized in this figure as fundamental contributions to the five "origins": (a) origin of the universe, (b) origin of the elements, (c) origin of the solar system, (d) origin of life, and (e) origin of advanced intelligence.
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Cosmology is a subject that borders on and sometimes merges with philosophy and religion. Since antiquity, the deep mysteries of the universe have intrigued mankind. Who are we? Where do we come from? What are we made of? Is the development of advanced intelligence capable of comprehending the grand design of the cosmos, the ultimate purpose of the universe? Is there life elsewhere in the universe? Is ours the only advanced intelligence or the most advanced intelligence in the universe? These questions have motivated great thinkers to pursue what Einstein called "the highest wisdom and the most radiant beauty." In the fourth century B.C., the essence of the cosmological question was formulated by the philosopher Chuang Tzu:… If there was a beginning, then there was a time before that beginning. And a time before the time which was before the time of that beginning. If there is existence, there must have been non-existence. And if there was a time when nothing existed, then there must be a time before that—when even nothing did not exist. Suddenly, when nothing came into existence, could one really say whether it belonged to the category of existence or of nonexistence? Even the very words I have just uttered, I cannot say whether they have really been uttered or not. There is nothing under the canopy of heaven greater than the tip of an autumn hair. A vast mountain is a small thing. Neither is there any age greater than that of a child cut off in infancy. P'eng Tsu [a Chinese Methuselah] himself died young. The universe and I came into being together; and I, and everything therein, are one. … Fortunately, our subject matter, solar system chemistry, is less esoteric than the questions asked by Chuang Tzu. A schematic diagram showing the principal pathways by which our solar system is formed is given in figure 4.1. The great triumphs of modern science have been summarized in this figure as fundamental contributions to the five "origins": (a) origin of the universe, (b) origin of the elements, (c) origin of the solar system, (d) origin of life, and (e) origin of advanced intelligence.
Magnus Paulsen Hansen
- Published in print:
- 2019
- Published Online:
- May 2020
- ISBN:
- 9781447349969
- eISBN:
- 9781447350156
- Item type:
- chapter
- Publisher:
- Policy Press
- DOI:
- 10.1332/policypress/9781447349969.003.0001
- Subject:
- Political Science, Public Policy
The introduction argues for the relevance of looking into the moral repertoire of ALMP reforms in public debates. The chapter argues for why the study of ideas and morality is pivotal to understand ...
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The introduction argues for the relevance of looking into the moral repertoire of ALMP reforms in public debates. The chapter argues for why the study of ideas and morality is pivotal to understand (and criticize) the political implications of ALMP reforms. Hereafter, the chapter engages critically with two sets of literatures. Firstly, scholars that have tried to theorize the varieties within the active turn, and secondly, with existing conceptualisations of the role of ideas and morality in relation to political and institutional changes. The last part of the chapter outlines a non-normative, but critical, approach (Hansen 2016) which deliberately refuses to evaluate the performance or judge the normative standards of ALMP in order to map the plurality of ideas related to ALMPs, as well as how these sediment into the everyday governing of the unemployed.Less
The introduction argues for the relevance of looking into the moral repertoire of ALMP reforms in public debates. The chapter argues for why the study of ideas and morality is pivotal to understand (and criticize) the political implications of ALMP reforms. Hereafter, the chapter engages critically with two sets of literatures. Firstly, scholars that have tried to theorize the varieties within the active turn, and secondly, with existing conceptualisations of the role of ideas and morality in relation to political and institutional changes. The last part of the chapter outlines a non-normative, but critical, approach (Hansen 2016) which deliberately refuses to evaluate the performance or judge the normative standards of ALMP in order to map the plurality of ideas related to ALMPs, as well as how these sediment into the everyday governing of the unemployed.
Christof Koch
- Published in print:
- 1998
- Published Online:
- November 2020
- ISBN:
- 9780195104912
- eISBN:
- 9780197562338
- Item type:
- chapter
- Publisher:
- Oxford University Press
- DOI:
- 10.1093/oso/9780195104912.003.0015
- Subject:
- Computer Science, Mathematical Theory of Computation
The cornerstone of modern biophysics is the comprehensive analysis by Hodgkin and Huxley (1952a,b,c,d) of the generation and propagation of action potentials in the ...
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The cornerstone of modern biophysics is the comprehensive analysis by Hodgkin and Huxley (1952a,b,c,d) of the generation and propagation of action potentials in the squid giant axon. The basis of their model is a fast sodium current INa and a delayed potassium current IK (which here we also refer to as IDR)- The last 40 years of research have shown that impulse conduction along axons can be successfully analyzed in terms of one or both of these currents. Nonetheless, their equations do not capture—nor were they intended to capture—a number of important biophysical phenomena, such as adaptation of the firing frequency to long-lasting stimuli or bursting, that is, the generation of two to five spikes within 5-20 msec. Moreover, the transmission of electrical signals within and between neurons involves more than the mere circulation of stereotyped pulses. These impulses must be set up and generated by subthreshold processes. The differences between the firing behavior of most neurons and the squid giant axon reflect the roles of other voltage-dependent ionic conductances than the two described by Hodgkin and Huxley. Over the last two decades, more than several dozen membrane conductances have been characterized (Hagiwara, 1983; Llinás, 1988; Hille, 1992). They differ in principal carrier, voltage, and time dependence, dependence on the presence of intracellular calcium and on their susceptibility to modulation by synaptic inputs and second messengers. Our knowledge of these conductances and the role they play in impulse formation has accelerated rapidly in recent years as a result of various technical innovations such as single-cell isolation, patch clamping, and molecular techniques. We will here describe the most important of these conductances and briefly characterize each one. In order to understand more completely the functional role of these conductances in determining the response of the cell to input, empirical equations that approximate their behavior under physiological conditions must be developed and compared against the physiological preparations. In a remarkable testimony to the power and the generality of the Hodgkin-Huxley approach, the majority of such phenomenological models has used their methodology of describing individual ionic conductances in terms of activating and inactivating particles with first-order kinetics (see Chap. 6).
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The cornerstone of modern biophysics is the comprehensive analysis by Hodgkin and Huxley (1952a,b,c,d) of the generation and propagation of action potentials in the squid giant axon. The basis of their model is a fast sodium current INa and a delayed potassium current IK (which here we also refer to as IDR)- The last 40 years of research have shown that impulse conduction along axons can be successfully analyzed in terms of one or both of these currents. Nonetheless, their equations do not capture—nor were they intended to capture—a number of important biophysical phenomena, such as adaptation of the firing frequency to long-lasting stimuli or bursting, that is, the generation of two to five spikes within 5-20 msec. Moreover, the transmission of electrical signals within and between neurons involves more than the mere circulation of stereotyped pulses. These impulses must be set up and generated by subthreshold processes. The differences between the firing behavior of most neurons and the squid giant axon reflect the roles of other voltage-dependent ionic conductances than the two described by Hodgkin and Huxley. Over the last two decades, more than several dozen membrane conductances have been characterized (Hagiwara, 1983; Llinás, 1988; Hille, 1992). They differ in principal carrier, voltage, and time dependence, dependence on the presence of intracellular calcium and on their susceptibility to modulation by synaptic inputs and second messengers. Our knowledge of these conductances and the role they play in impulse formation has accelerated rapidly in recent years as a result of various technical innovations such as single-cell isolation, patch clamping, and molecular techniques. We will here describe the most important of these conductances and briefly characterize each one. In order to understand more completely the functional role of these conductances in determining the response of the cell to input, empirical equations that approximate their behavior under physiological conditions must be developed and compared against the physiological preparations. In a remarkable testimony to the power and the generality of the Hodgkin-Huxley approach, the majority of such phenomenological models has used their methodology of describing individual ionic conductances in terms of activating and inactivating particles with first-order kinetics (see Chap. 6).
David Fisher
- Published in print:
- 2010
- Published Online:
- November 2020
- ISBN:
- 9780195393965
- eISBN:
- 9780197562796
- Item type:
- chapter
- Publisher:
- Oxford University Press
- DOI:
- 10.1093/oso/9780195393965.003.0013
- Subject:
- Chemistry, History of Chemistry
Because, you know how it is, you never forget your first love. I tried, believe me, I tried. I turned enthusiastically to activation analysis, which is a technique in ...
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Because, you know how it is, you never forget your first love. I tried, believe me, I tried. I turned enthusiastically to activation analysis, which is a technique in which you irradiate a sample in a nuclear reactor—which, unlike the Cosmotron, just sits there day and night pouring out neutrons which slip into the sample, hardly disturbing it but pushing some of the atoms over the line from stable to radioactive. Since radioactivity is the most sensitive detection type of them all, you can measure the presence of extremely small amounts of many elements in the most complex of minerals. Roman Schmitt of General Atomic (later at Oregon State University) and I had discussed the possibility of detecting some elements without any work. You would just drop the sample in the reactor and then stick it in one of those newfangled multichannel gamma detectors. There would be a whole mélange of gamma rays coming out from all the radioactive isotopes in the sample, but a few elements throw out gammas of very high energy, and these would stand out above the background noise, or so we thought. The data would give immediate results while we just sat there reading a book or daydreaming. For instance, aluminum. It consists of a single isotope, 27Al, and upon bathing it in a sea of neutrons it forms 28Al, which is radioactive with a half-life of 2.3 minutes and a gamma ray of 1.78 Mev. Beautiful! Hardly any element throws out a gamma of energy more than 1 Mev, so the 1.78 bugger would stand out easily, and the 2.3-minute half-life meant that I could easily follow its decay for positive identification. Several half-lives, or, say, ten minutes, would be plenty. By irradiating a sample of known aluminum content, a comparison of the two activities would give the aluminum in the unknown. What every scientist dreams about: the ten-minute experiment! The problem was to find some reason to measure aluminum.
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Because, you know how it is, you never forget your first love. I tried, believe me, I tried. I turned enthusiastically to activation analysis, which is a technique in which you irradiate a sample in a nuclear reactor—which, unlike the Cosmotron, just sits there day and night pouring out neutrons which slip into the sample, hardly disturbing it but pushing some of the atoms over the line from stable to radioactive. Since radioactivity is the most sensitive detection type of them all, you can measure the presence of extremely small amounts of many elements in the most complex of minerals. Roman Schmitt of General Atomic (later at Oregon State University) and I had discussed the possibility of detecting some elements without any work. You would just drop the sample in the reactor and then stick it in one of those newfangled multichannel gamma detectors. There would be a whole mélange of gamma rays coming out from all the radioactive isotopes in the sample, but a few elements throw out gammas of very high energy, and these would stand out above the background noise, or so we thought. The data would give immediate results while we just sat there reading a book or daydreaming. For instance, aluminum. It consists of a single isotope, 27Al, and upon bathing it in a sea of neutrons it forms 28Al, which is radioactive with a half-life of 2.3 minutes and a gamma ray of 1.78 Mev. Beautiful! Hardly any element throws out a gamma of energy more than 1 Mev, so the 1.78 bugger would stand out easily, and the 2.3-minute half-life meant that I could easily follow its decay for positive identification. Several half-lives, or, say, ten minutes, would be plenty. By irradiating a sample of known aluminum content, a comparison of the two activities would give the aluminum in the unknown. What every scientist dreams about: the ten-minute experiment! The problem was to find some reason to measure aluminum.
Douglass Taber
- Published in print:
- 2011
- Published Online:
- November 2020
- ISBN:
- 9780199764549
- eISBN:
- 9780197563090
- Item type:
- chapter
- Publisher:
- Oxford University Press
- DOI:
- 10.1093/oso/9780199764549.003.0031
- Subject:
- Chemistry, Organic Chemistry
To assemble the framework of the cytotoxic macrolide Amphidinolide X 3, Fèlix Urpí and Jaume Vilarrasa of the Universitat de Barcelona devised (Organic Lett. 2008, 10, ...
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To assemble the framework of the cytotoxic macrolide Amphidinolide X 3, Fèlix Urpí and Jaume Vilarrasa of the Universitat de Barcelona devised (Organic Lett. 2008, 10, 5191) the ring-closing metathesis of the alkenyl silane 1. No Ru catalyst was effective, but the Schrock Mo catalyst worked well. In the course of a synthesis of (-)-Dactylolide 6, Michael P. Jennings of the University of Alabama offered (J. Org. Chem. 2008, 73, 5965) a timely reminder of the particular reactivity of allylic alcohols in ring-closing metathesis. The cyclization of 4 to 5 proceeded smoothly, but attempted ring closing of the corresponding bis silyl ether failed. Polyenes such as ( + )-Cytotrienin A 8 are notoriously unstable. It is remarkable that Yujiro Hayashi of the Tokyo University of Science could (Angew. Chem. Int. Ed. 2008, 47, 6657) assemble the triene of 8 by the ring-closing metathesis of the highly functionalized precursor 7. Bicyclo [2.2.2] structures such as 9 are readily available by the addition of, in this case, methyl acrylate to an enantiomerically-pure 2-methylated dihydropyridine. André B. Charette of the Université de Montréal found (J. Am. Chem. Soc. 2008, 130, 13873) that 9 responded well to ring-opening/ring-closing metathesis, to give the octahydroquinoline 10. Functional group manipulation converted 10 into the Clavelina alkaloid ( + )-Lepadin B 11. The construction of trisubstituted alkenes by ring-closing metathesis can be difficult, and medium rings with their transannular strain are notoriously challenging to form. Nevertheless, Karl-Heinz Altmann of the ETH Zürich was able (Angew. Chem. Int. Ed. 2008, 47, 10081), using the H2 catalyst, to cyclize 12 to cyclononene 13, the precursor to the Xenia lactone ( + )-Blumiolide C 14. It is noteworthy that these fi ve syntheses used four different metathesis catalysts in the key alkene forming step. For the cyclization of 7, the use of the Grubbs first generation catalyst G1, that couples terminal alkenes but tends not to interact with internal alkenes, was probably critical to success.
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To assemble the framework of the cytotoxic macrolide Amphidinolide X 3, Fèlix Urpí and Jaume Vilarrasa of the Universitat de Barcelona devised (Organic Lett. 2008, 10, 5191) the ring-closing metathesis of the alkenyl silane 1. No Ru catalyst was effective, but the Schrock Mo catalyst worked well. In the course of a synthesis of (-)-Dactylolide 6, Michael P. Jennings of the University of Alabama offered (J. Org. Chem. 2008, 73, 5965) a timely reminder of the particular reactivity of allylic alcohols in ring-closing metathesis. The cyclization of 4 to 5 proceeded smoothly, but attempted ring closing of the corresponding bis silyl ether failed. Polyenes such as ( + )-Cytotrienin A 8 are notoriously unstable. It is remarkable that Yujiro Hayashi of the Tokyo University of Science could (Angew. Chem. Int. Ed. 2008, 47, 6657) assemble the triene of 8 by the ring-closing metathesis of the highly functionalized precursor 7. Bicyclo [2.2.2] structures such as 9 are readily available by the addition of, in this case, methyl acrylate to an enantiomerically-pure 2-methylated dihydropyridine. André B. Charette of the Université de Montréal found (J. Am. Chem. Soc. 2008, 130, 13873) that 9 responded well to ring-opening/ring-closing metathesis, to give the octahydroquinoline 10. Functional group manipulation converted 10 into the Clavelina alkaloid ( + )-Lepadin B 11. The construction of trisubstituted alkenes by ring-closing metathesis can be difficult, and medium rings with their transannular strain are notoriously challenging to form. Nevertheless, Karl-Heinz Altmann of the ETH Zürich was able (Angew. Chem. Int. Ed. 2008, 47, 10081), using the H2 catalyst, to cyclize 12 to cyclononene 13, the precursor to the Xenia lactone ( + )-Blumiolide C 14. It is noteworthy that these fi ve syntheses used four different metathesis catalysts in the key alkene forming step. For the cyclization of 7, the use of the Grubbs first generation catalyst G1, that couples terminal alkenes but tends not to interact with internal alkenes, was probably critical to success.
Douglass Taber
- Published in print:
- 2011
- Published Online:
- November 2020
- ISBN:
- 9780199764549
- eISBN:
- 9780197563090
- Item type:
- chapter
- Publisher:
- Oxford University Press
- DOI:
- 10.1093/oso/9780199764549.003.0057
- Subject:
- Chemistry, Organic Chemistry
The sedative alkaloid paliurine F 7 is a pentapeptide bridged by an arene. Gwilherm Evano of the Université de Versailles took advantage of this in his synthesis ...
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The sedative alkaloid paliurine F 7 is a pentapeptide bridged by an arene. Gwilherm Evano of the Université de Versailles took advantage of this in his synthesis (Angew. Chem. Int. Ed. 2007, 46, 572) of 7, although it was necessary to prepare, from serine, one of the amino acid derivatives, the protected 3-hydroxyprolinol 2. The key step in the synthesis was the Cu-catalyzed intramolecular coupling of 5 to give the macrolactam 6. Deprotection and acylation then gave paliurine F 7. Lepadiformine 14, isolated from the tunicate Clavelina lepadiformis, shows moderate cytotoxicity, and is also a K+ channel blocker. The synthesis of 14 (Angew. Chem. Int. Ed. 2007, 46, 2631) by Donald Craig of Imperial College started with the aziridine 8, prepared from the corresponding epoxide. Opening of the protected aziridine with the anion of methyl phenyl sulfone set the stage for condensation of the dianion derived from 9 with the aldehyde 10, to give, with high diastereocontrol, the amine 11. Deprotection followed by cyclization then led to the activated ether 12. While the opening of 12 with an alkyl Grignard reagent proceeded with undesired inversion at the reacting center, opening with the alkynyl Grignard delivered mainly the desired 13. Reduction followed by oxidation, epimerization and reduction then gave lepadiformine 14. The Amaryllidaceae alkaloid 7-deoxypancratistatin 21 has potent antiviral activity. A challenge in the assembly of 21 is that the ring fusion is trans, less stable than the corresponding cis diastereomer. The synthesis of 21 (J. Org. Chem. 2007, 72, 2570) by Albert Padwa of Emory University started with 17, the preparation of which by the combination 15 and 16 he had previously reported in the course of his synthesis of lycoricidine (OHL December 11, 2006). Ester 17 had the desired trans ring fusion, but with an angular ester substituent that had to be removed. While it would be expected from the mechanism that Rh-mediated decarbonylation of an aldehyde would proceed with retention of absolute configuration, and this had been confirmed experimentally, this reaction had not been applied to such a challenging substrate. In the event, the transformation proceeded smoothly, to give the desired trans 19. Dehydration and dihydroxylation of 19 led to the cyclic sulfate 20, selective SN2 opening of which delivered 7-deoxypancratistatin 21.
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The sedative alkaloid paliurine F 7 is a pentapeptide bridged by an arene. Gwilherm Evano of the Université de Versailles took advantage of this in his synthesis (Angew. Chem. Int. Ed. 2007, 46, 572) of 7, although it was necessary to prepare, from serine, one of the amino acid derivatives, the protected 3-hydroxyprolinol 2. The key step in the synthesis was the Cu-catalyzed intramolecular coupling of 5 to give the macrolactam 6. Deprotection and acylation then gave paliurine F 7. Lepadiformine 14, isolated from the tunicate Clavelina lepadiformis, shows moderate cytotoxicity, and is also a K+ channel blocker. The synthesis of 14 (Angew. Chem. Int. Ed. 2007, 46, 2631) by Donald Craig of Imperial College started with the aziridine 8, prepared from the corresponding epoxide. Opening of the protected aziridine with the anion of methyl phenyl sulfone set the stage for condensation of the dianion derived from 9 with the aldehyde 10, to give, with high diastereocontrol, the amine 11. Deprotection followed by cyclization then led to the activated ether 12. While the opening of 12 with an alkyl Grignard reagent proceeded with undesired inversion at the reacting center, opening with the alkynyl Grignard delivered mainly the desired 13. Reduction followed by oxidation, epimerization and reduction then gave lepadiformine 14. The Amaryllidaceae alkaloid 7-deoxypancratistatin 21 has potent antiviral activity. A challenge in the assembly of 21 is that the ring fusion is trans, less stable than the corresponding cis diastereomer. The synthesis of 21 (J. Org. Chem. 2007, 72, 2570) by Albert Padwa of Emory University started with 17, the preparation of which by the combination 15 and 16 he had previously reported in the course of his synthesis of lycoricidine (OHL December 11, 2006). Ester 17 had the desired trans ring fusion, but with an angular ester substituent that had to be removed. While it would be expected from the mechanism that Rh-mediated decarbonylation of an aldehyde would proceed with retention of absolute configuration, and this had been confirmed experimentally, this reaction had not been applied to such a challenging substrate. In the event, the transformation proceeded smoothly, to give the desired trans 19. Dehydration and dihydroxylation of 19 led to the cyclic sulfate 20, selective SN2 opening of which delivered 7-deoxypancratistatin 21.
Douglass Taber
- Published in print:
- 2011
- Published Online:
- November 2020
- ISBN:
- 9780199764549
- eISBN:
- 9780197563090
- Item type:
- chapter
- Publisher:
- Oxford University Press
- DOI:
- 10.1093/oso/9780199764549.003.0063
- Subject:
- Chemistry, Organic Chemistry
Several new methods have been put forward for the functionalization of benzene derivatives. J. S. Yadav of the Indian Institute of Chemical Technology, Hyderabad has ...
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Several new methods have been put forward for the functionalization of benzene derivatives. J. S. Yadav of the Indian Institute of Chemical Technology, Hyderabad has devised (Chem. Lett. 2008, 37, 652) a procedure for direct thiocyanation, converting 1 into 2. Sukbok Chang of KAIST has established (Chem. Commun. 2008, 3052) that both NH4Cl and aqueous NH3 could be used to directly aminate an aryl iodide such as 3. John F. Hartwig of the University of Illinois has developed (J. Am. Chem. Soc. 2008, 130, 7534) a protocol for the directed borylation of anilines such as 5 and of phenols, based on a transient silylation. Karsten Menzel of Merck West Point (Tetrahedron Lett. 2008, 49, 415) has observed selective exchange of tribromobenzene derivatives such as 7, with the direction of the selectivity being controlled by the fourth substituent on the benzene. Gary A. Molander of the University of Pennsylvania has extensively developed the stable, readily prepared trifluoroborates, exemplified by 10 (J. Org. Chem. 2008, 73, 2052) and 14 (Organic Lett. 2008, 10, 1795) as partners for Suzuki-Miyaura coupling. The conversion of 9 to 10 is complementary to aminocarbonylation, exemplified by the conversion of 12 to 13 reported (Tetrahedron Lett. 2008, 49, 2221) by Bhalchandra M. Bhanage of the Institute of Chemical Technology, University of Mumbai. The coupling of 9 with 14 is complementary to the long-known Heck coupling of an aryl halide such as 16 with an allylic alcohol, as illustrated by the preparation of 18 described (Tetrahedron Lett. 2008, 49, 3279) by Martin E. Maier of the Universität Tübingen. Professor Hartwig has also (Organic Lett. 2008, 10, 1545, 1549) optimized conditions for the Pd-catalyzed arylation of ester enolates such as 19. Gang Zhou of Schering-Plough, Kenilworth, NJ has developed (Organic Lett. 2008, 10, 2517) a related transformation, the arylation of deprotonated sulfonamides. Peter Somfai of the Royal Institute of Technology, Stockholm has established (Angew. Chem. Int. Ed. 2008, 47, 1907) a complementary procedure, base-mediated elimination of t -butoxide from 24, followed by 1,2-addition of an aryl or heteroaryl Grignard reagent.
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Several new methods have been put forward for the functionalization of benzene derivatives. J. S. Yadav of the Indian Institute of Chemical Technology, Hyderabad has devised (Chem. Lett. 2008, 37, 652) a procedure for direct thiocyanation, converting 1 into 2. Sukbok Chang of KAIST has established (Chem. Commun. 2008, 3052) that both NH4Cl and aqueous NH3 could be used to directly aminate an aryl iodide such as 3. John F. Hartwig of the University of Illinois has developed (J. Am. Chem. Soc. 2008, 130, 7534) a protocol for the directed borylation of anilines such as 5 and of phenols, based on a transient silylation. Karsten Menzel of Merck West Point (Tetrahedron Lett. 2008, 49, 415) has observed selective exchange of tribromobenzene derivatives such as 7, with the direction of the selectivity being controlled by the fourth substituent on the benzene. Gary A. Molander of the University of Pennsylvania has extensively developed the stable, readily prepared trifluoroborates, exemplified by 10 (J. Org. Chem. 2008, 73, 2052) and 14 (Organic Lett. 2008, 10, 1795) as partners for Suzuki-Miyaura coupling. The conversion of 9 to 10 is complementary to aminocarbonylation, exemplified by the conversion of 12 to 13 reported (Tetrahedron Lett. 2008, 49, 2221) by Bhalchandra M. Bhanage of the Institute of Chemical Technology, University of Mumbai. The coupling of 9 with 14 is complementary to the long-known Heck coupling of an aryl halide such as 16 with an allylic alcohol, as illustrated by the preparation of 18 described (Tetrahedron Lett. 2008, 49, 3279) by Martin E. Maier of the Universität Tübingen. Professor Hartwig has also (Organic Lett. 2008, 10, 1545, 1549) optimized conditions for the Pd-catalyzed arylation of ester enolates such as 19. Gang Zhou of Schering-Plough, Kenilworth, NJ has developed (Organic Lett. 2008, 10, 2517) a related transformation, the arylation of deprotonated sulfonamides. Peter Somfai of the Royal Institute of Technology, Stockholm has established (Angew. Chem. Int. Ed. 2008, 47, 1907) a complementary procedure, base-mediated elimination of t -butoxide from 24, followed by 1,2-addition of an aryl or heteroaryl Grignard reagent.
Douglass Taber
- Published in print:
- 2011
- Published Online:
- November 2020
- ISBN:
- 9780199764549
- eISBN:
- 9780197563090
- Item type:
- chapter
- Publisher:
- Oxford University Press
- DOI:
- 10.1093/oso/9780199764549.003.0080
- Subject:
- Chemistry, Organic Chemistry
Benjamin List of the Max Planck Institute, Mülheim devised (J. Am. Chem. Soc. 2008, 130, 6070) a chiral primary amine salt that catalyzed the enantioselective ...
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Benjamin List of the Max Planck Institute, Mülheim devised (J. Am. Chem. Soc. 2008, 130, 6070) a chiral primary amine salt that catalyzed the enantioselective epoxidation of cyclohexenone 1 . Larger ring and alkyl-substituted enones are also epoxidized with high ee. Three- and four-membered rings are versatile intermediates for further transformation. Tsutomu Katsuki of Kyushu University developed (Angew. Chem. Int. Ed. 2008, 47, 2450) an elegant Al(salalen) catalyst for the enantioselective Simmons-Smith cyclopropanation of allylic alcohols such as 3. Kazuaki Ishihara of Nagoya University found (J. Am. Chem. Soc. 2007, 129, 8930) chiral amine salts that effected enantioselective 2+2 cycloaddition of α-acyloxyacroleins such as 5 to alkenes to give the cyclobutane 7 with high enantio- and diastereocontrol. Gideon Grogan of the University of York overexpressed (Adv. Synth. Cat. 2008, 349, 916) the enzyme 6-oxocamphor hydrolase in E. coli . The 6-OCH so prepared converted prochiral diketones such as 8 to the cyclopentane 9 in high ee. Richard P. Hsung of the University of Wisconsin found (Organic Lett. 2008, 10, 661) that the carbene produced by oxidation of the ynamide 10 cyclized to 11 with high de. Teck-Peng Loh of Nanyang Technological University extended (J. Am. Chem. Soc. 2008, 130, 7194) butane-2,3-diol directed cyclization to the preparation of the cyclopentane 15. Note that sidechain relative configuration is also controlled. We established (J. Org. Chem. 2008, 73, 3467) that the thermal ene reaction of 17 delivered the tetrasubstituted cyclopentane 18 as a single diastereomer. Tony K. M. Shing of the Chinese University of Hong Kong devised (J. Org. Chem. 2007, 72, 6610) a simple protocol for the conversion of carbohydrate-derived lactones such as 19 to the highly-substituted, enantiomerically-pure cyclohexenone 21. Hiromichi Fujioka and Yasuyuki Kita of Osaka University established (Organic Lett. 2007, 9, 5605) a chiral diol-mediated conversion of the cyclohexadiene 22 to the diastereomerically pure cyclohexenone 24. Dirk Trauner, now of the University of Munich, reported (Organic Lett. 2008, 10, 149) an elegant assembly of the neuritogenic polyketide shimalactone A 28.
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Benjamin List of the Max Planck Institute, Mülheim devised (J. Am. Chem. Soc. 2008, 130, 6070) a chiral primary amine salt that catalyzed the enantioselective epoxidation of cyclohexenone 1 . Larger ring and alkyl-substituted enones are also epoxidized with high ee. Three- and four-membered rings are versatile intermediates for further transformation. Tsutomu Katsuki of Kyushu University developed (Angew. Chem. Int. Ed. 2008, 47, 2450) an elegant Al(salalen) catalyst for the enantioselective Simmons-Smith cyclopropanation of allylic alcohols such as 3. Kazuaki Ishihara of Nagoya University found (J. Am. Chem. Soc. 2007, 129, 8930) chiral amine salts that effected enantioselective 2+2 cycloaddition of α-acyloxyacroleins such as 5 to alkenes to give the cyclobutane 7 with high enantio- and diastereocontrol. Gideon Grogan of the University of York overexpressed (Adv. Synth. Cat. 2008, 349, 916) the enzyme 6-oxocamphor hydrolase in E. coli . The 6-OCH so prepared converted prochiral diketones such as 8 to the cyclopentane 9 in high ee. Richard P. Hsung of the University of Wisconsin found (Organic Lett. 2008, 10, 661) that the carbene produced by oxidation of the ynamide 10 cyclized to 11 with high de. Teck-Peng Loh of Nanyang Technological University extended (J. Am. Chem. Soc. 2008, 130, 7194) butane-2,3-diol directed cyclization to the preparation of the cyclopentane 15. Note that sidechain relative configuration is also controlled. We established (J. Org. Chem. 2008, 73, 3467) that the thermal ene reaction of 17 delivered the tetrasubstituted cyclopentane 18 as a single diastereomer. Tony K. M. Shing of the Chinese University of Hong Kong devised (J. Org. Chem. 2007, 72, 6610) a simple protocol for the conversion of carbohydrate-derived lactones such as 19 to the highly-substituted, enantiomerically-pure cyclohexenone 21. Hiromichi Fujioka and Yasuyuki Kita of Osaka University established (Organic Lett. 2007, 9, 5605) a chiral diol-mediated conversion of the cyclohexadiene 22 to the diastereomerically pure cyclohexenone 24. Dirk Trauner, now of the University of Munich, reported (Organic Lett. 2008, 10, 149) an elegant assembly of the neuritogenic polyketide shimalactone A 28.
Douglass Taber
- Published in print:
- 2011
- Published Online:
- November 2020
- ISBN:
- 9780199764549
- eISBN:
- 9780197563090
- Item type:
- chapter
- Publisher:
- Oxford University Press
- DOI:
- 10.1093/oso/9780199764549.003.0089
- Subject:
- Chemistry, Organic Chemistry
Often, 6,6-spiroketals such as Spirofungin A 3 have a strong anomeric bias. Spirofungin A does not, as the epimer favored by double anomeric stabilization suffers from ...
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Often, 6,6-spiroketals such as Spirofungin A 3 have a strong anomeric bias. Spirofungin A does not, as the epimer favored by double anomeric stabilization suffers from destabilizing steric interactions. In his synthesis of 3, Sergey A. Kozmin of the University of Chicago took advantage (Angew. Chem. Int. Ed. 2007, 46, 8854) of the normally-destablizing spatial proximity of the two alkyl branches of 3, joining them with a siloxy linker to assure the anomeric preference of the spiroketal. The assembly of 1 showcased the power of asymmetric crotylation, and of Professor Kozmin’s linchpin cyclopropenone ketal cross metathesis. To achieve the syn relative (and absolute) configuration of 6, commercial cis-2-butene was metalated, then condensed with the Brown (+)-MeOB(Ipc)2 auxiliary. The accompanying Supporting Information, accessible via the online HTML version of the journal article, includes a succinct but detailed procedure for carrying out this homologation. For the anti relative (and absolute) configuration of 9, it is more convenient to use the tartrate 8 introduced by Roush. Driven by the release of the ring strain inherent in 10, ring opening cross metathesis with 6 proceeded to give the 1:1 adduct 11 in near quantitative yield. The derived cross-linked silyl ether 12 underwent smooth ring-closing metathesis to the dienone 1. On hydogenation, the now-flexible ring system could fold into the spiro ketal. With the primary and secondary alcohols bridged by the linking silyl ether, only one anomeric form, 2, of the spiro ketal was energetically accessible. A remaining challenge was the stereocontrolled construction of the trisubstituted alkene. To this end, the aldehyde 13 was homologated to the dibromide 14. Pd-mediated coupling of the alkenyl stannane 15 with 14 was selective for the E bromide. The residual Z bromide was then coupled with Zn(CH3)2 to give 16. These steps, and the final steps to complete the construction of spirofungin A 3 , could be carried out without exposure to equilibrating acid, so the carefully established spiro ketal confi guration was maintained.
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Often, 6,6-spiroketals such as Spirofungin A 3 have a strong anomeric bias. Spirofungin A does not, as the epimer favored by double anomeric stabilization suffers from destabilizing steric interactions. In his synthesis of 3, Sergey A. Kozmin of the University of Chicago took advantage (Angew. Chem. Int. Ed. 2007, 46, 8854) of the normally-destablizing spatial proximity of the two alkyl branches of 3, joining them with a siloxy linker to assure the anomeric preference of the spiroketal. The assembly of 1 showcased the power of asymmetric crotylation, and of Professor Kozmin’s linchpin cyclopropenone ketal cross metathesis. To achieve the syn relative (and absolute) configuration of 6, commercial cis-2-butene was metalated, then condensed with the Brown (+)-MeOB(Ipc)2 auxiliary. The accompanying Supporting Information, accessible via the online HTML version of the journal article, includes a succinct but detailed procedure for carrying out this homologation. For the anti relative (and absolute) configuration of 9, it is more convenient to use the tartrate 8 introduced by Roush. Driven by the release of the ring strain inherent in 10, ring opening cross metathesis with 6 proceeded to give the 1:1 adduct 11 in near quantitative yield. The derived cross-linked silyl ether 12 underwent smooth ring-closing metathesis to the dienone 1. On hydogenation, the now-flexible ring system could fold into the spiro ketal. With the primary and secondary alcohols bridged by the linking silyl ether, only one anomeric form, 2, of the spiro ketal was energetically accessible. A remaining challenge was the stereocontrolled construction of the trisubstituted alkene. To this end, the aldehyde 13 was homologated to the dibromide 14. Pd-mediated coupling of the alkenyl stannane 15 with 14 was selective for the E bromide. The residual Z bromide was then coupled with Zn(CH3)2 to give 16. These steps, and the final steps to complete the construction of spirofungin A 3 , could be carried out without exposure to equilibrating acid, so the carefully established spiro ketal confi guration was maintained.
Russell K. Skowronek, M. James Blackman, and Ronald L. Bishop
- Published in print:
- 2014
- Published Online:
- January 2015
- ISBN:
- 9780813049816
- eISBN:
- 9780813050232
- Item type:
- book
- Publisher:
- University Press of Florida
- DOI:
- 10.5744/florida/9780813049816.001.0001
- Subject:
- Archaeology, Historical Archaeology
This volume contains a wealth of new information on the production, supply, and exchange of pottery in Alta California, which will be useful for years to come. Using the framework of World Systems ...
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This volume contains a wealth of new information on the production, supply, and exchange of pottery in Alta California, which will be useful for years to come. Using the framework of World Systems Theory and Instrumental Neutron Activation Analysis, the authors have demonstrated the widespread production of both plain and glazed ceramics in Spanish California and the supply of other ceramic tablewares from Mexico. When situated with the other contributions to this book, the nuanced story of ceramics, the people who made them, and the nuclear and other scientists who studied them reveals a sophistication that far surpasses the wildest dreams of mission-era archaeology.Less
This volume contains a wealth of new information on the production, supply, and exchange of pottery in Alta California, which will be useful for years to come. Using the framework of World Systems Theory and Instrumental Neutron Activation Analysis, the authors have demonstrated the widespread production of both plain and glazed ceramics in Spanish California and the supply of other ceramic tablewares from Mexico. When situated with the other contributions to this book, the nuanced story of ceramics, the people who made them, and the nuclear and other scientists who studied them reveals a sophistication that far surpasses the wildest dreams of mission-era archaeology.
Russell K. Skowronek, M. James Blackman, and Ronald L. Bishop
- Published in print:
- 2014
- Published Online:
- January 2015
- ISBN:
- 9780813049816
- eISBN:
- 9780813050232
- Item type:
- chapter
- Publisher:
- University Press of Florida
- DOI:
- 10.5744/florida/9780813049816.003.0012
- Subject:
- Archaeology, Historical Archaeology
Over 23,000 Brown Ware sherds, most undecorated, were recovered during excavations at several mid-nineteenth-century archaeological sites in Old Town San Diego State Historic Park. Diagnostic sherds ...
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Over 23,000 Brown Ware sherds, most undecorated, were recovered during excavations at several mid-nineteenth-century archaeological sites in Old Town San Diego State Historic Park. Diagnostic sherds (especially rim fragments) from the entire collection, as well as all specimens from a single well-defined context, were examined and provide the basis for interpretation of vessel production, form, and use. INNA (Instrumental Neutron Activation Analysis) and petrographic thin section results are also reviewed. These studies demonstrate that precontact Native American ceramic fabrication and vessel form traditions predominated in the Mexican Republic and early America eras (i.e. 1830s–1850s), although there were some relatively subtle changes in temper and firing. A possible clay source is discussed, and historic records of Indian servants in the Mexican period pueblo of San Diego are explored.Less
Over 23,000 Brown Ware sherds, most undecorated, were recovered during excavations at several mid-nineteenth-century archaeological sites in Old Town San Diego State Historic Park. Diagnostic sherds (especially rim fragments) from the entire collection, as well as all specimens from a single well-defined context, were examined and provide the basis for interpretation of vessel production, form, and use. INNA (Instrumental Neutron Activation Analysis) and petrographic thin section results are also reviewed. These studies demonstrate that precontact Native American ceramic fabrication and vessel form traditions predominated in the Mexican Republic and early America eras (i.e. 1830s–1850s), although there were some relatively subtle changes in temper and firing. A possible clay source is discussed, and historic records of Indian servants in the Mexican period pueblo of San Diego are explored.
Brian P. McLaughlin
- Published in print:
- 2014
- Published Online:
- September 2014
- ISBN:
- 9780262027236
- eISBN:
- 9780262322461
- Item type:
- chapter
- Publisher:
- The MIT Press
- DOI:
- 10.7551/mitpress/9780262027236.003.0002
- Subject:
- Philosophy, Philosophy of Mind
After spelling out the systematicity challenge to connectionism, I examine Paul Smolensky and Géraldine Legendre's attempt to meet the challenge by appeal to a kind of architecture that they label ...
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After spelling out the systematicity challenge to connectionism, I examine Paul Smolensky and Géraldine Legendre's attempt to meet the challenge by appeal to a kind of architecture that they label “an integrated connectionist/symbolic architecture.” I argue that although their response to the systematicity challenge is of considerable interest, it fails to meet the challenge.Less
After spelling out the systematicity challenge to connectionism, I examine Paul Smolensky and Géraldine Legendre's attempt to meet the challenge by appeal to a kind of architecture that they label “an integrated connectionist/symbolic architecture.” I argue that although their response to the systematicity challenge is of considerable interest, it fails to meet the challenge.
Silke Bothfeld and Sigrid Betzelt
- Published in print:
- 2013
- Published Online:
- January 2014
- ISBN:
- 9781447312741
- eISBN:
- 9781447312857
- Item type:
- chapter
- Publisher:
- Policy Press
- DOI:
- 10.1332/policypress/9781447312741.003.0013
- Subject:
- Social Work, Social Policy
While employment regulation is clearly lagging behind the development of insecure employment practices, as Silke Bothfeld and Sigrid Betzelt's chapter indicates, social protection policy is shoring ...
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While employment regulation is clearly lagging behind the development of insecure employment practices, as Silke Bothfeld and Sigrid Betzelt's chapter indicates, social protection policy is shoring up their expansion. In reconsidering the decommodifying effects of social policy in the contemporary work-welfare nexus, the authors’ use of the concept of ‘autonomy’ provides an alternative means to establish the impact of changes in a state-citizen relations located in the rise of ‘activation’ policies, and the primacy now accorded to full labour market participation. In a cross-national European comparison, their focus is the nature and form of activation policies and how these affect individual autonomy, measured by quality, status differentiation and user participation in the process of employment-related social security reform. In their overview of labour market deregulation, changes to active labour market policies and unemployment benefit schemes, the analysis demonstrates a general decline in both the quality and security afforded by employment; a trend that is accelerated by both the policy push for maximum participation and the demise of the ‘core worker’ as a referent of standards.Less
While employment regulation is clearly lagging behind the development of insecure employment practices, as Silke Bothfeld and Sigrid Betzelt's chapter indicates, social protection policy is shoring up their expansion. In reconsidering the decommodifying effects of social policy in the contemporary work-welfare nexus, the authors’ use of the concept of ‘autonomy’ provides an alternative means to establish the impact of changes in a state-citizen relations located in the rise of ‘activation’ policies, and the primacy now accorded to full labour market participation. In a cross-national European comparison, their focus is the nature and form of activation policies and how these affect individual autonomy, measured by quality, status differentiation and user participation in the process of employment-related social security reform. In their overview of labour market deregulation, changes to active labour market policies and unemployment benefit schemes, the analysis demonstrates a general decline in both the quality and security afforded by employment; a trend that is accelerated by both the policy push for maximum participation and the demise of the ‘core worker’ as a referent of standards.