94 research outputs found
A mechanistic and cautionary case study on the use of alternating potential in electrochemical reactions
A mechanistic study on use of alternating potential (i. e. electrode polarity switching) in synthetic organic electrochemical method development using the IKA ElectraSyn 2.0 is described. Unexpected product selectivity challenges revealed that alternating potential facilitated direct, rather than mediated, electrochemical benzylic C−H oxidation of toluene derivatives. Whilst constant potential irrespective of the direction of electrode polarity was expected, our in-depth analysis revealed changes in the magnitude of applied potential with periodic switching of electrode polarity. These findings highlight an equipment engineering concern that is likely to influence and inform optimization strategies for a wide range of synthetic organic electrochemical methods under development
Photo-catalytic carboxylate to sulfinamide switching delivers a divergent synthesis of sulfonamides and sulfonimidamides
Sulfinamides, sulfonamides, and sulfonimidamides are in-demand motifs in medicinal chemistry, yet methods for the synthesis of alkyl variants that start from simple, readily available feedstocks are scarce. In addition, bespoke syntheses of each class of molecules are usually needed. In this report, we detail the synthesis of these three distinct sulfur functional groups, using readily available and structurally diverse alkyl carboxylic acids as the starting materials. The method harnesses alkyl radical generation from carboxylic acids using acridine photocatalysts and 400 nm light with subsequent radical addition to sulfinylamine reagents, delivering sulfinamide products. Using the N-alkoxy sulfinylamine reagent t-BuO-NSO as the radical trap provides common N-alkoxy sulfinamide intermediates, which can be converted in a divergent manner to either sulfonamides or sulfonimidamides, by treatment with sodium hydroxide, or an amine, respectively. The reactions are scalable, tolerate a broad range of functional groups, and can be used for the diversification of complex biologically active compounds
The Theoretical Astrophysical Observatory: Cloud-Based Mock Galaxy Catalogues
We introduce the Theoretical Astrophysical Observatory (TAO), an online
virtual laboratory that houses mock observations of galaxy survey data. Such
mocks have become an integral part of the modern analysis pipeline. However,
building them requires an expert knowledge of galaxy modelling and simulation
techniques, significant investment in software development, and access to high
performance computing. These requirements make it difficult for a small
research team or individual to quickly build a mock catalogue suited to their
needs. To address this TAO offers access to multiple cosmological simulations
and semi-analytic galaxy formation models from an intuitive and clean web
interface. Results can be funnelled through science modules and sent to a
dedicated supercomputer for further processing and manipulation. These modules
include the ability to (1) construct custom observer light-cones from the
simulation data cubes; (2) generate the stellar emission from star formation
histories, apply dust extinction, and compute absolute and/or apparent
magnitudes; and (3) produce mock images of the sky. All of TAO's features can
be accessed without any programming requirements. The modular nature of TAO
opens it up for further expansion in the future.Comment: 17 pages, 11 figures, 2 tables; accepted for publication in ApJS. The
Theoretical Astrophysical Observatory (TAO) is now open to the public at
https://tao.asvo.org.au/. New simulations, models and tools will be added as
they become available. Contact [email protected] if you have data you
would like to make public through TAO. Feedback and suggestions are very
welcom
Synthesis of Tetrahydroxyazepanes from Shikimic Acid
The 13th International Electronic Conference on Synthetic Organic Chemistry session General Organic SynthesisWe describe herein a novel synthetical application of shikimic acid, which consist of its transformation into (3R,4S,5R,7S)-7-(hydroxymethyl)azepane-3,4,5-triolWe thank the Spanish Ministry Science and Innovation and the Xunta de Galicia for financial suppor
Semi-Analytic Galaxy Evolution (SAGE): Model Calibration and Basic Results
This paper describes a new publicly available codebase for modelling galaxy
formation in a cosmological context, the "Semi-Analytic Galaxy Evolution"
model, or SAGE for short. SAGE is a significant update to that used in Croton
et al. (2006) and has been rebuilt to be modular and customisable. The model
will run on any N-body simulation whose trees are organised in a supported
format and contain a minimum set of basic halo properties. In this work we
present the baryonic prescriptions implemented in SAGE to describe the
formation and evolution of galaxies, and their calibration for three N-body
simulations: Millennium, Bolshoi, and GiggleZ. Updated physics include: gas
accretion, ejection due to feedback, and reincorporation via the galactic
fountain; a new gas cooling--radio mode active galactic nucleus (AGN) heating
cycle; AGN feedback in the quasar mode; a new treatment of gas in satellite
galaxies; and galaxy mergers, disruption, and the build-up of intra-cluster
stars. Throughout, we show the results of a common default parameterization on
each simulation, with a focus on the local galaxy population.Comment: 15 pages, 9 figures, accepted for publication in ApJS. SAGE is a
publicly available codebase for modelling galaxy formation in a cosmological
context, available at https://github.com/darrencroton/sage Questions and
comments can be sent to Darren Croton: [email protected]
Et3SiH + KOtBu provide multiple reactive intermediates that compete in the reactions and rearrangements of benzylnitriles and indolenines
The combination of potassium tert-butoxide and triethylsilane is unusual because it generates multiple different types of reactive intermediates simultaneously that provide access to (i) silyl radical reactions, (ii) hydrogen atom transfer reactions to closed shell molecules and to radicals, (iii) electron transfer reductions and (iv) hydride ion chemistry, giving scope for unprecedented outcomes. Until now, reactions with this reagent pair have generally been explained by reference to one of the intermediates, but we now highlight the interplay and competition between them
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