Regioselective Dihalohydration Reactions of Propargylic Alcohols: Gold-Catalyzed and Non-Catalyzed Reactions

The regioselective conversion of propargylic alcohols into previously unreported α,α-diiodo-β-hydroxyketones was achieved by treatment with N-iodosuccinimide in the presence of a gold catalyst. The corresponding α,α-dichloro-β-hydroxyketones were obtained by treatment with trichloroisocyanuric acid in the absence of a catalyst. The latter reaction can be extended to other alkynols. These transformations can be used to prepare potentially useful halogenated building blocks. Preliminary mechanistic studies suggest that the reaction involves participation of the acetonitrile solvent in the formation of a 5-halo-1,3-oxazine intermediate

Intramolecular amidocyclopropanation reactions using diethoxymethyl-functionalised lactams as organozinc carbenoid precursors

Intramolecular amidocyclopropanation reactions of diethoxymethyl-lactams containing a pendant alkene were examined using zinc/TMSCI. With a range of 4-6-membered lactams, bicyclic amidocyclopropanes were obtained with very high diastereoselectivity with a preference for the formation of the More hindered endo-cyclopropane. (C) 2009 Elsevier Ltd. All rights reserved

Synthesis of substituted benzooxaborinin-1-ols via palladium-catalysed cyclisation of alkenyl- and alkynyl-boronic acids

Two new palladium-catalysed reactions have been developed for the synthesis of stable 4-substituted benzooxaborinin-1-ols. A palladium-catalysed cyclisation of ortho-alkenylbenzene boronic acids can be used to access 4-chlorobenzooxaborinin-1-ols via a Wacker-type oxidation and chlorination. Alternatively, ortho-alkynylbenzene boronic acids undergo a palladium-catalysed oxyallylation reaction to provide 4-allylbenzooxaborinin-1-ols

A lactate-derived chiral aldehyde for determining the enantiopurity of enantioenriched primary amines

In this paper we describe the use of a chiral aldehyde derived from lactate esters for determining the enantiopurity of primary amines, via the formation of diastereomeric imines. The method was shown to be suitable for reproducibly determining the enantiopurity of a diverse set of chiral amines. Both enantiomers of the aldehyde can be prepared in two steps from commercially available materials

Motional timescale predictions by molecular dynamics simulations: Case study using proline and hydroxyproline sidechain dynamics.

We propose a new approach for force field optimisations which aims at reproducing dynamics characteristics using biomolecular MD simulations, in addition to improved prediction of motionally averaged structural properties available from experiment. As the source of experimental data for dynamics fittings, we use (13) C NMR spin-lattice relaxation times T1 of backbone and sidechain carbons, which allow to determine correlation times of both overall molecular and intramolecular motions. For structural fittings, we use motionally averaged experimental values of NMR J couplings. The proline residue and its derivative 4-hydroxyproline with relatively simple cyclic structure and sidechain dynamics were chosen for the assessment of the new approach in this work. Initially, grid search and simplexed MD simulations identified large number of parameter sets which fit equally well experimental J couplings. Using the Arrhenius-type relationship between the force constant and the correlation time, the available MD data for a series of parameter sets were analyzed to predict the value of the force constant that best reproduces experimental timescale of the sidechain dynamics. Verification of the new force-field parameters against NMR J couplings and correlation times showed consistent and significant improvements compared to the original force field in reproducing both structural and dynamics properties. The results suggest that matching experimental timescales of motions together with motionally averaged characteristics is the valid approach for force field parameter optimisation. Such a comprehensive approach is not restricted to cyclic residues and can be extended to other amino acid residues, as well as to the backbone. © Proteins 2013;. © 2013 Wiley Periodicals, Inc

Dihalohydration of Alkynols: A Versatile Approach to Diverse Halogenated Molecules

In this paper we outline how dihalohydration reactions of propargylic alcohols can be used to access a wide variety of useful halogenated building blocks. A novel procedure for dibromohydration of alkynes has been developed, and a selection of dichloro and dibromo diols and cyclic ethers were synthesized. The dihalohydration of homo‐propargylic alcohols provides a useful route to 3‐halofurans, which were shown to readily undergo cycloaddition reactions under mild conditions. Finally, a novel ring‐expansion of propargylic alcohols containing a cyclopropylalkyne provides access to halogenated alkenylcyclobutanes

Bacterial microevolution and the Pangenome

The comparison of multiple genome sequences sampled from a bacterial population reveals considerable diversity in both the core and the accessory parts of the pangenome. This diversity can be analysed in terms of microevolutionary events that took place since the genomes shared a common ancestor, especially deletion, duplication, and recombination. We review the basic modelling ingredients used implicitly or explicitly when performing such a pangenome analysis. In particular, we describe a basic neutral phylogenetic framework of bacterial pangenome microevolution, which is not incompatible with evaluating the role of natural selection. We survey the different ways in which pangenome data is summarised in order to be included in microevolutionary models, as well as the main methodological approaches that have been proposed to reconstruct pangenome microevolutionary history

Diversity and Distribution of Symbiodinium Associated with Seven Common Coral Species in the Chagos Archipelago, Central Indian Ocean

The Chagos Archipelago designated as a no-take marine protected area in 2010, lying about 500 km south of the Maldives in the Indian Ocean, has a high conservation priority, particularly because of its fast recovery from the ocean-wide massive coral mortality following the 1998 coral bleaching event. The aims of this study were to examine Symbiodinium diversity and distribution associated with scleractinian corals in five atolls of the Chagos Archipelago, spread over 10,000 km 2. Symbiodinium clade diversity in 262 samples of seven common coral species, Acropora muricata, Isopora palifera, Pocillopora damicornis, P. verrucosa, P. eydouxi, Seriatopora hystrix, and Stylophora pistillata were determined using PCR-SSCP of the ribosomal internal transcribed spacer 1 (ITS1), PCR-DDGE of ITS2, and phylogenetic analyses. The results indicated that Symbiodinium in clade C were the dominant symbiont group in the seven coral species. Our analysis revealed types of Symbiodinium clade C specific to coral species. Types C1 and C3 (with C3z and C3i variants) were dominant in Acroporidae and C1 and C1c were the dominant types in Pocilloporidae. We also found 2 novel ITS2 types in S. hystrix and 1 novel ITS2 type of Symbiodinium in A. muricata. Some colonies of A. muricata and I. palifera were also associated with Symbiodinium A1. These results suggest that corals in the Chagos Archipelago host different assemblages of Symbiodinium types then their conspecifics from other locations in the Indian Ocean; and that future research will show whether these patterns in Symbiodinium genotypes may be due to local adaptation to specific conditions in the Chagos

Instability of Plastid DNA in the Nuclear Genome

Functional gene transfer from the plastid (chloroplast) and mitochondrial genomes to the nucleus has been an important driving force in eukaryotic evolution. Non-functional DNA transfer is far more frequent, and the frequency of such transfers from the plastid to the nucleus has been determined experimentally in tobacco using transplastomic lines containing, in their plastid genome, a kanamycin resistance gene (neo) readymade for nuclear expression. Contrary to expectations, non-Mendelian segregation of the kanamycin resistance phenotype is seen in progeny of some lines in which neo has been transferred to the nuclear genome. Here, we provide a detailed analysis of the instability of kanamycin resistance in nine of these lines, and we show that it is due to deletion of neo. Four lines showed instability with variation between progeny derived from different areas of the same plant, suggesting a loss of neo during somatic cell division. One line showed a consistent reduction in the proportion of kanamycin-resistant progeny, suggesting a loss of neo during meiosis, and the remaining four lines were relatively stable. To avoid genomic enlargement, the high frequency of plastid DNA integration into the nuclear genome necessitates a counterbalancing removal process. This is the first demonstration of such loss involving a high proportion of recent nuclear integrants. We propose that insertion, deletion, and rearrangement of plastid sequences in the nuclear genome are important evolutionary processes in the generation of novel nuclear genes. This work is also relevant in the context of transgenic plant research and crop production, because similar processes to those described here may be involved in the loss of plant transgenes

Monazite trumps zircon: applying SHRIMP U–Pb geochronology to systematically evaluate emplacement ages of leucocratic, low-temperature granites in a complex Precambrian orogen

Although zircon is the most widely used geochronometer to determine the crystallisation ages of granites, it can be unreliable for low-temperature melts because they may not crystallise new zircon. For leucocratic granites U–Pb zircon dates, therefore, may reflect the ages of the source rocks rather than the igneous crystallisation age. In the Proterozoic Capricorn Orogen of Western Australia, leucocratic granites are associated with several pulses of intracontinental magmatism spanning ~800 million years. In several instances, SHRIMP U–Pb zircon dating of these leucocratic granites either yielded ages that were inconclusive (e.g., multiple concordant ages) or incompatible with other geochronological data. To overcome this we used SHRIMP U–Th–Pb monazite geochronology to obtain igneous crystallisation ages that are consistent with the geological and geochronological framework of the orogen. The U–Th–Pb monazite geochronology has resolved the time interval over which two granitic supersuites were emplaced; a Paleoproterozoic supersuite thought to span ~80 million years was emplaced in less than half that time (1688–1659 Ma) and a small Meso- to Neoproterozoic supersuite considered to have been intruded over ~70 million years was instead assembled over ~130 million years and outlasted associated regional metamorphism by ~100 million years. Both findings have consequences for the duration of associated orogenic events and any estimates for magma generation rates. The monazite geochronology has contributed to a more reliable tectonic history for a complex, long-lived orogen. Our results emphasise the benefit of monazite as a geochronometer for leucocratic granites derived by low-temperature crustal melting and are relevant to other orogens worldwide