Abstract The asymmetric alkylation of acyclic ketones is a longstanding challenge in organic synthesis. Reported herein are diastereoselective and enantioselective allylic substitutions with acyclic α‐alkoxy ketones catalyzed by a metallacyclic iridium complex to form products with contiguous stereogenic centers derived from the nucleophile and electrophile. These reactions occur between allyl methyl carbonates and unstabilized copper(I) enolates generated in situ from acyclic α‐alkoxy ketones. The resulting products can be readily converted into enantioenriched tertiary alcohols and tetrahydrofuran derivatives without erosion of enantiomeric purity.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTrimethylsilyl derivatives of bis(cyclopentadienyl)zirconium and -hafnium. Crystal structure of (.eta.5-C5H5)2Zr(SiMe3)(S2CNEt2)T. Don TilleyCite this: Organometallics 1985, 4, 8, 1452–1457Publication Date (Print):August 1, 1985Publication History Published online1 May 2002Published inissue 1 August 1985https://doi.org/10.1021/om00127a025Request reuse permissionsArticle Views333Altmetric-Citations70LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (775 KB) Get e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts
Blunted growth hormone (GH) release in response to stimulation by a secretagogue has been widely reported in both children and adults with anxiety and depressive disorders. Blunted GH responsiveness appears to be a stable characteristic of an individual, suggesting that it may be useful as a biological marker that would allow early recognition of these disease processes. Another potential biological marker for anxiety disorders is the temperamental construct of behavioral inhibition. Children identified as being behaviorally inhibited early in life are more likely than less inhibited children to suffer from anxiety disorders later in life (Biederman et al. 1993; Hirshfeld et al. 1992). If blunted GH responsiveness to pharmacological challenge and behavioral inhibition are markers of anxiety and depressive disorders, then it would follow that they would coexist in a subset of individuals. However, such prospective studies in clinically normal young children are difficult to perform. Therefore, in this study, we examined GH responsiveness and temperament in a group of 38 young rhesus monkeys (ages 3-6 months). Monkeys received an intravenous dose of 10 microg/kg of growth hormone-releasing hormone (GHRH) and 5 microg/kg of clonidine, combined, to assess GH response to stimulation. Behavioral reactivity in a fearful situation was assessed using the Human Intruder Test developed by Kalin et al. (1991). This test measures response to a potentially threatening stimulus (a human stranger making direct eye contact). Results showed a population distribution of GH response to GHRH and clonidine ranging from 120 ng/mL/90 minutes to 3,000 ng/mL/90 minutes. There was no difference in GH response in males versus females or any significant effect of age on GH response. There was a significant correlation between GH responsiveness and the time spent reacting to the intruder in the Human Intruder Test. Monkeys with lower GH responsiveness reacted less to the intruder (p < 0.01). Additionally, when monkeys were classified based on their reactivity in the Human Intruder Test, behaviorally nonreactive monkeys had significantly lower GH responsiveness than behaviorally reactive monkeys (p < 0.005). These data provide evidence that there are inherent differences in GH responsiveness to stimulation in young rhesus monkeys and that low GH responsiveness is linked to low behavioral reactivity, which may be a form of behavioral inhibition. Further studies will be necessary to determine if the characteristics of low GH responsiveness and low behavioral reactivity predict an increased propensity to develop anxious or depressive behaviors over the course of the life span.
The suspension copolymerization of several t-butoxycarbonyl (t-BOC) protected 4-vinyl phenols with divinylbenzene has been studied to produce high porosity 10 μm bead materials with surface areas of 200–300 m2/g for use as separation media. The choice and amount of porogen is critical for the control of porosity and surface area while particle size and size distribution is controlled by other reaction variables. The t-BOC protecting groups of the polymers are easily removed by thermolysis and the deprotected beads are useful in the separation of amines. The relationship between polymer structure and separation ability in h.p.l.c. has been explored and the effect of alkyl substituents located ortho to the phenolic groups is discussed.
We present photometry of 12 recent supernovae (SNe) recovered in a {\it Hubble Space Telescope} Snapshot program, and tie the measurements to earlier ground-based observations, in order to study the late-time evolution of the SNe. Many of the ground-based measurements are previously unpublished, and were made primarily with a robotic telescope, the Katzman Automatic Imaging Telescope. Evidence for circumstellar interaction is common among the core-collapse SNe. Late-time decline rates for Type IIn SNe are found to span a wide range, perhaps due to differences in circumstellar interaction. An extreme case, SN IIn 1995N, declined by only 1.2 mag in $V$ over about 4 years following discovery. Template images of some SNe must therefore be obtained many years after the explosion, if contamination from the SN itself is to be minimized. Evidence is found against a previous hypothesis that the Type IIn SN 1997bs was actually a superoutburst of a luminous blue variable star. The peculiar SN Ic 1997ef, a "hypernova," declined very slowly at late times. The decline rate of the SN Ia 2000cx decreased at late times, but this is unlikely to have been caused by a light echo.
Detailed potential/pH stability diagrams for the lithium‐water system at 25°C have been derived as part of a program to describe the electrochemistry of the lithium anode in aqueous alkaline environments. The diagrams include lithium hydride as a stable solid phase at sufficiently negative potentials, and it is postulated that the passive film on Li in contact with concentrated alkaline solutions, under open‐circuit conditions, comprises a LiH barrier layer covered with a hydrated LiOH outer layer. The postulated existence of as a barrier layer, under open‐circuit conditions, is inconsistent with the thermodynamic data for metallic lithium in contact with concentrated LiOH and LiOH + KOH solutions. © 1999 The Electrochemical Society. All rights reserved.
Plant natural products have been used for centuries to treat human illnesses, as recreational substances, and as flavoring and coloring agents in our food. Nowadays, commercial-scale manufacturing of plant natural products using extraction from natural resources or chemical synthesis poses challenges for environmental sustainability, such as species overexploitation. Bio-based synthesis of plant natural products in microbial cell factories can offer an attractive alternative as these processes reduce the use of natural plant resources and instead rely on renewable feedstocks as raw materials. Here, we review the most recent developments on the sustainable supply of plant natural products by the bio-based synthesis in yeast, with a special focus on newly discovered and implemented plant natural product biosynthetic pathways, approaches for chemical diversification of natural products, and optimization of platform yeast cell factories. From this, we discuss environmental considerations and the main challenges toward sustainable and robust microbial production of plant natural products based on fermentation.
Metformin, dimethylbiguanide, is an agent that has been widely used in the treatment of non-insulin-dependent diabetes mellitus. Its mechanism of action is not dependent on the stimulation of insulin secretion, unlike the sulfonylureas. It is clear that metformin reduces fasting endogenous glucose production rates, which are elevated in non-insulin-dependent diabetes mellitus. Some studies have proposed that metformin reduces endogenous glucose production primarily by reducing gluconeogenesis, whereas others have proposed that gluconeogenesis is not affected. The authors review the literature regarding the effects of metformin on hepatic carbohydrate metabolism.