Enantioselective Intramolecular Michael Addition of Nitronates onto Conjugated Esters: Access to Cyclic γ-Amino Acids with up to Three Stereocenters

A highly stereoselective synthesis of conformationally constrained cyclic γ-amino acids has been devised. The key step involves an intramolecular cyclization of a nitronate onto a conjugated ester, promoted by a bifunctional thiourea catalyst. This methodology has been successfully applied to generate a variety of γ-amino acids, including some containing three contiguous stereocenters, with very high diastereoselectivity and excellent enantioselectivity. It is postulated that an interaction that is key to the success of the process is the simultaneous coordination of the thiourea functionality to both the conjugated ester and the nitronate. Finally, the synthetic utility of these compounds is demonstrated in the synthesis of two dipeptides derived from the C- and N-termini.

Investigations on the effect of amino acids on acrylamide, pyrazines, and Michael addition products in model systems

Acrylamide and pyrazine formation, as influenced by the incorporation of different amino acids, was investigated in sealed low-moisture asparagine-glucose model systems. Added amino acids, with the exception of glycine and cysteine and at an equimolar concentration to asparagine, increased the rate of acrylamide formation. The strong correlation between the unsubstituted pyrazine and acrylamide suggests the promotion of the formation of Maillard reaction intermediates, and in particular glyoxal, as the determining mode of-action. At increased amino acid concentrations, diverse effects were observed. The initial rates of acrylamide formation remained high for valine, alanine, phenylalanine, tryptophan, glutamine, and Ieucine, while a significant mitigating effect, as evident from the acrylamide yields after 60 min of heating at 160 degrees C, was observed for proline, tryptophan, glycine, and cysteine. The secondary amine containing amino acids, proline and tryptophan, had the most profound mitigating effect on acrylamide after 60 min of heating. The relative importance of the competing effect of added amino acids for alpha-dicarbonyls and acrylamide-amino, acid alkylation reactions is discussed and accompanied by data on the relative formation rates of selected amino acid-AA adducts.

A homo-proline tetrazole as an improved organocatalyst for the asymmetric Michael addition of carbonyl compounds to nitro-olefins

A new homo-proline tetrazole derivative 7 has been prepared and shown to have improved properties for achieving asymmetric Michael addition of carbonyl compounds to nitro-olefins.

Asymmetric synthesis using catalysts containing multiple stereogenic centres and a trans-1,2-diaminocyclohexane core; reversal of predominant enantioselectivity upon N-alkylation

N-Methylation of ligands containing a trans-1,2-diaminocyclohexane core and multiple stereogenic centres is shown to provide the product of the opposite configuration in significant enantiomeric excess, in the addition of diethylzinc to aldehydes. Some of the ligands were effective in an asymmetric Michael addition. (C) 2004 Elsevier Ltd. All rights reserved.

Asymmetric phase-transfer-catalyzed synthesis of five-membered cyclic gamma-Amino acid precursors

The first example of an intramolecular enantioselective Michael addition of nitronates onto conjugated systems utilizing a chiral phase-transfer catalyst is described. A range of five-membered gamma-nitro esters with up to three stereocentres have been prepared and the relative and absolute configurations proven by chemical and crystallographic methods. The products are rapidly obtained and are precursors to five-membered cyclic gamma-amino acids.

Towards the total synthesis of mycaperoxide B: probing biosynthetic rationale

Studies towards the biomimetic synthesis of mycaperoxide B (1) are described. We have established the synthesis of four diastereoisomers of mycaperoxide B methyl ester (1a) by employing a Michael addition across an α,β-unsaturated ester precursor 2 as the key step. This result strongly suggestsstereocontrol in the addition of the hydroperoxide functionality to the E double bond and discloses the importance of choosing the correct geometry of the α,β-unsaturated double bond when attempting to synthesise mycaperoxide B. Four diastereoisomeric tetrahydrofurans derived from an intramolecular rearrangement of the 1,2-dioxolane enolate 12 were also isolated and characterised.

Metal cluster expansion by addition of low valent group 14 reagents: III. Reaction of bis[bis(trimethylsilyl)methyl]tin with M3(CO)12 or its derivatives (M = Fe, Ru, or Os): the crystal and molecular structures of M3(μ-SnR2)2(CO)10(R = CH(SiMe3)2; M = Ru or Os)

The stannylene [SnR2] (R = CH(SiMe3)2) reacts in different ways with the three dodecacarbonyls of the iron triad: [Fe3(CO)12] gives [Fe2(CO)8(μ-SnR2)], [Ru3(CO)12] gives the planar pentametallic cluster [Ru3(CO)10(μ-SnR2)2], for which a full structural analysis is reported, while [Os3(CO)12] fails to react. Different products are also obtained from three nitrile derivatives: [Fe3-(CO)11(MeCN)] gives [Fe2(CO)6(μ-SnR2)2], which has a structure significantly different from that of known Fe2Sn2 clusters, [Ru3(CO)10(MeCN)2] gives the pentametallic cluster described above, while [Os3(CO)10(MeCN)2] gives the isostructural osmium analogue, which shows the unusual feature of a CO group bridging two osmium atoms.

Reversible addition of CO to coordinatively unsaturated high-spin iron(II) complexes

Several new coordinatively unsaturated iron(II) complexes of the types [Fe(EN-iPr)X2] (E = P, S, Se; X = Cl, Br) and [Fe(ON-iPr)2X]X containing bidentate EN ligands based on N-(2-pyridinyl)aminophosphines as well as oxo, thio, and seleno derivatives thereof were prepared and characterized by NMR spectroscopy and X-ray crystallography. Mössbauer spectroscopy and magnetization studies confirmed their high-spin nature with magnetic moments very close to 4.9 μB, reflecting the expected four unpaired d-electrons in all these compounds. Stable low-spin carbonyl complexes of the types [Fe(PN-iPr)2(CO)X]X (X = Cl, Br) and cis-CO,cis-Br-[Fe(PN-iPr)(CO)2X2] (X = Br) were obtained by reacting cis-Fe(CO)4X2 with the stronger PN donor ligands, but not with the weaker EN donor ligands (E = O, S, Se). Furthermore, the reactivity of [Fe(PN-iPr)X2] toward CO was investigated by IR spectroscopy. Whereas at room temperature no reaction took place, at −50 °C [Fe(PN-iPr)X2] added readily CO to form, depending on the nature of X, the mono- and dicarbonyl complexes [Fe(PN-iPr)(X)2(CO)] (X = Cl) and [Fe(PN-iPr)(CO)2X2] (X = Cl, Br), respectively. In the case of X = Br, two isomeric dicarbonyl complexes, namely, cis-CO,trans-Br-[Fe(PN-iPr)(CO)2Br2] (major species) and cis-CO,cis-Br-[Fe(PN-iPr)(CO)2Br2] (minor species), are formed. The addition of CO to [Fe(PN-iPr)X2] was investigated in detail by means of DFT/B3LYP calculations. This study strongly supports the experimental findings that at low temperature two isomeric low-spin dicarbonyl complexes are formed. For kinetic reasons cis,trans-[Fe(PN-iPr)(CO)2Br2] releases CO at elevated temperature, re-forming [Fe(PN-iPr)Br2], while the corresponding cis,cis isomer is stable under these conditions.

Methods and resources for climate impacts research: achieving synergy

The prediction of climate variability and change requires the use of a range of simulation models. Multiple climate model simulations are needed to sample the inherent uncertainties in seasonal to centennial prediction. Because climate models are computationally expensive, there is a tradeoff between complexity, spatial resolution, simulation length, and ensemble size. The methods used to assess climate impacts are examined in the context of this trade-off. An emphasis on complexity allows simulation of coupled mechanisms, such as the carbon cycle and feedbacks between agricultural land management and climate. In addition to improving skill, greater spatial resolution increases relevance to regional planning. Greater ensemble size improves the sampling of probabilities. Research from major international projects is used to show the importance of synergistic research efforts. The primary climate impact examined is crop yield, although many of the issues discussed are relevant to hydrology and health modeling. Methods used to bridge the scale gap between climate and crop models are reviewed. Recent advances include large-area crop modeling, quantification of uncertainty in crop yield, and fully integrated crop–climate modeling. The implications of trends in computer power, including supercomputers, are also discussed.

An Integrated Assessment of changes in the thermohaline circulation

This paper discusses the risks of a shutdown of the thermohaline circulation (THC) for the climate system, for ecosystems in and around the North Atlantic as well as for fisheries and agriculture by way of an Integrated Assessment. The climate model simulations are based on greenhouse gas scenarios for the 21st century and beyond. A shutdown of the THC, complete by 2150, is triggered if increased freshwater input from inland ice melt or enhanced runoff is assumed. The shutdown retards the greenhouse gas-induced atmospheric warming trend in the Northern Hemisphere, but does not lead to a persistent net cooling. Due to the simulated THC shutdown the sea level at the North Atlantic shores rises by up to 80 cm by 2150, in addition to the global sea level rise. This could potentially be a serious impact that requires expensive coastal protection measures. A reduction of marine net primary productivity is associated with the impacts of warming rather than a THC shutdown. Regional shifts in the currents in the Nordic Seas could strongly deteriorate survival chances for cod larvae and juveniles. This could lead to cod fisheries becoming unprofitable by the end of the 21st century. While regional socioeconomic impacts might be large, damages would be probably small in relation to the respective gross national products. Terrestrial ecosystem productivity is affected much more by the fertilization from the increasing CO2 concentration than by a THC shutdown. In addition, the level of warming in the 22nd to 24th century favours crop production in northern Europe a lot, no matter whether the THC shuts down or not. CO2 emissions corridors aimed at limiting the risk of a THC breakdown to 10% or less are narrow, requiring departure from business-as-usual in the next few decades. The uncertainty about THC risks is still high. This is seen in model analyses as well as in the experts’ views that were elicited. The overview of results presented here is the outcome of the Integrated Assessment project INTEGRATION.

Quantifying carbon-cycle feedbacks

Perturbations to the carbon cycle could constitute large feedbacks on future changes in atmospheric CO2 concentration and climate. This paper demonstrates how carbon cycle feedback can be expressed in formally similar ways to climate feedback, and thus compares their magnitudes. The carbon cycle gives rise to two climate feedback terms: the concentration–carbon feedback, resulting from the uptake of carbon by land and ocean as a biogeochemical response to the atmospheric CO2 concentration, and the climate–carbon feedback, resulting from the effect of climate change on carbon fluxes. In the earth system models of the Coupled Climate–Carbon Cycle Model Intercomparison Project (C4MIP), climate–carbon feedback on warming is positive and of a similar size to the cloud feedback. The concentration–carbon feedback is negative; it has generally received less attention in the literature, but in magnitude it is 4 times larger than the climate–carbon feedback and more uncertain. The concentration–carbon feedback is the dominant uncertainty in the allowable CO2 emissions that are consistent with a given CO2 concentration scenario. In modeling the climate response to a scenario of CO2 emissions, the net carbon cycle feedback is of comparable size and uncertainty to the noncarbon–climate response. To quantify simulated carbon cycle feedbacks satisfactorily, a radiatively coupled experiment is needed, in addition to the fully coupled and biogeochemically coupled experiments, which are referred to as coupled and uncoupled in C4MIP. The concentration–carbon and climate–carbon feedbacks do not combine linearly, and the concentration–carbon feedback is dependent on scenario and time.

Solar induced climate effects

Solar electromagnetic radiation powers Earth’s climate system and, consequently, it is often naively assumed that changes in this solar output must be responsible for changes in Earth’s climate. However, the Sun is close to a blackbody radiator and so emits according to its surface temperature and the huge thermal time constant of the outer part of the Sun limits the variability in surface temperature and hence output. As a result, on all timescales of interest, changes in total power output are limited to small changes in effective surface temperature (associated with magnetic fields) and potential, although as yet undetected, solar radius variations. Larger variations are seen in the UV part of the spectrum which is emitted from the lower solar atmosphere (the chromosphere) and which influences Earth’s stratosphere. There is interest in“top-down” mechanisms whereby solar UV irradiance modulates stratospheric temperatures and winds which, in turn, may influence the underlying troposphere where Earth’s climate and weather reside. This contrasts with “bottom-up” effects in which the small total solar irradiance (dominated by the visible and near-IR) variations cause surface temperature changes which drive atmospheric circulations. In addition to these electromagnetic outputs, the Sun modulates energetic particle fluxes incident on the Earth. Solar Energetic Particles (SEP) are emitted by solar flares and from the shock fronts ahead of supersonic (and super-Alfvenic) ejections of material from the solar atmosphere. These SEPs enhance the destruction of polar stratospheric ozone which could be an additional form of top-down climate forcing. Even more energetic are Galactic Cosmic Rays (GCRs). These particles are not generated by the Sun, rather they originate at the shock fronts emanating from violent galactic events such as supernovae explosions; however, the expansion of the solar magnetic field into interplanetary space means that the Sun modulates the number of GCRs reaching Earth. These play a key role in enabling Earth’s global electric (thunderstorm) circuit and it has been proposed that they also modulate the formation of clouds. Both electromagnetic and corpuscular solar effects are known to vary over the solar magnetic cycle which is typically between 10 and 14 yrs in length (with an average close to 11 yrs). The solar magnetic field polarity at any one phase of one of these activity cycles is opposite to that at the same phase of the next cycle and this influences some phenomena, for example GCRs, which therefore show a 22 yr (“Hale”) cycle on average. Other phenomena, such as irradiance modulation, do not depend on the polarity of the magnetic field and so show only the basic 11-yr activity cycle. However, any effects on climate are much more significant for solar drifts over centennial timescales. This chapter discusses and evaluates potential effects on Earth’s climate system of variations in these solar inputs. Because of the great variety of proposed mechanisms, the wide range of timescales studied (from days to millennia) and the many debates (often triggered by the application of inadequate statistical methods), the literature on this subject is vast, complex, divergent and rapidly changing: consequently the number of references cited in this review is very large (yet still only a small fraction of the total).

Simultaneous observations of reconnection pulses at Cluster and their effects on the cusp aurora seen at Chinese Yellow River Station

While the Cluster spacecraft were located near the high-latitude magnetopause, between 10:10 and 10:40 UT on 16 January 2004, three typical flux transfer event (FTE) signatures were observed. During this interval, simultaneous and conjugated all-sky camera measurements, recorded at Yellow River Station, Svalbard, are available at 630.0 and 557.7nm that show poleward-moving auroral forms (PMAFs), consistent with magnetic reconnection at dayside magnetopause. Simultaneous FTEs seen at the magnetopause mainly move northward, but having duskward (eastward) and tailward velocity components, roughly consistent with the observed direction of motion of the PMAFs in all-sky images. Between the PMAFs meridional keograms, extracted from the all-sky images, show intervals of lower intensity aurora which migrate equatorward just before the PMAFs intensify. This is strong evidence for an equatorward eroding and poleward moving open-closed boundary (OCB) associated with a variable magnetopause reconnection rate under variable IMF conditions. From the durations of the PMAFs we infer that the evolution time of FTEs is 5-11 minutes from its origin on magnetopause to its addition to the polar cap.