10,405 research outputs found
Recent trends in whole cell and isolated enzymes in enantioselective synthesis
Modern synthetic organic chemistry has experienced an enormous growth in biocatalytic methodologies; enzymatic transformations and whole cell bioconversions have become generally accepted synthetic tools for asymmetric synthesis. This review details an overview of the latest
achievements in biocatalytic methodologies for the synthesis of enantiopure compounds with a particular focus on chemoenzymatic synthesis in non-aqueous media, immobilisation technology and dynamic kinetic resolution. Furthermore, recent advances in ketoreductase technology and their applications are also presented
Asymmetric oxidation of sulfides
This review discusses synthesis of enantiopure sulfoxides through the asymmetric oxidation of prochiral sulfides. The use of metal complexes to promote asymmetric sulfoxidation is described in detail, with a particular emphasis on the synthesis of biologically active sulfoxides. The use of non-metal-based systems, such as oxaziridines, chiral hydroperoxides and peracids, as well as enzyme-catalyzed sulfoxidations is also examined
1,3-Dipolar cycloadditions of 2-thio-3-chloroacrylamides with nitrile oxides and nitrones
1,3-Dipolar cycloadditions of 2-thio-3-chloroacrylamides with nitrile oxides and nitrones is described. A series of novel isoxazolines are isolated from the nitrile oxide cycloadditions, whilst the isoxazolines generated from the nitrone cycloadditions undergo further ring opening to yield piperidines
Copper-catalyzed asymmetric oxidation of sulfides
Copper-catalyzed asymmetric sulfoxidation of aryl benzyl and aryl alkyl sulfides, using aqueous hydrogen peroxide as the oxidant, has been investigated. A relationship between the steric effects of the sulfide substituents and the enantioselectivity of the oxidation has been observed, with up to 93% ee for 2-naphthylmethyl phenyl sulfoxide, in modest yield in this instance (up to 30%). The influence of variation of solvent and ligand structure was examined, and the optimized conditions were then used to oxidize a number of aryl alkyl and aryl benzyl sulfides, producing sulfoxides in excellent yields in most cases (up to 92%), and good enantiopurities in certain cases (up to 84% ee)
1,3-Dipolar cycloadditions of 2-thio-3-chloroacrylamides with diazoalkanes
2-Thio-3-chloroacrylamides undergo 1,3-dipolar cycloadditions with diazoalkanes leading to a series of novel pyrazolines and pyrazoles. The mechanistic and synthetic features of the cycloadditions to the 2-thio-3-chloroacrylamides at both the sulfide and sulfoxide levels of oxidation are rationalised on the basis of the nature of the substituents
Diastereoselective sulfur oxidation of 2-thio-3-chloroacrylamides
Diastereoselective sulfur oxidation in 2-thio-3-chloroacrylamides is described. A range of chiral amine auxiliaries were incorporated in the β-chloroacrylamide, and the efficiency with which the stereochemistry was relayed to the sulfur centre during sulfoxidation was
investigated. Diastereomeric ratios of up to 3.3:1 were achieved
Synthesis of enantioenriched sulfoxides
This review discusses strategies for the asymmetric synthesis of sulfoxides, compounds with many applications in stereoselective synthesis and in some cases with pharmaceutical application. The review describes asymmetric oxidation, including metal catalyzed and non-metal and biological oxidation processes, in addition to synthetic approaches via nucleophilic substitution of appropriately substituted precursors. Kinetic resolution in oxidation of sulfoxides to the analogous sulfones is also discussed; in certain instances, access to enantioenriched sulfoxides can be achieved via a combination of asymmetric sulfide oxidation and complementary kinetic resolution in sulfoxide oxidation
The Rising Light Curves of Type Ia Supernovae
We present an analysis of the early, rising light curves of 18 Type Ia
supernovae (SNe Ia) discovered by the Palomar Transient Factory (PTF) and the
La Silla-QUEST variability survey (LSQ). We fit these early data flux using a
simple power-law to determine the time of first
light , and hence the rise-time from first light to
peak luminosity, and the exponent of the power-law rise (). We find a mean
uncorrected rise time of days, with individual SN rise-times
ranging from to days. The exponent n shows significant
departures from the simple 'fireball model' of (or ) usually assumed in the literature. With a mean value of , our data also show significant diversity from event to event. This
deviation has implications for the distribution of 56Ni throughout the SN
ejecta, with a higher index suggesting a lesser degree of 56Ni mixing. The
range of n found also confirms that the 56Ni distribution is not standard
throughout the population of SNe Ia, in agreement with earlier work measuring
such abundances through spectral modelling. We also show that the duration of
the very early light curve, before the luminosity has reached half of its
maximal value, does not correlate with the light curve shape or stretch used to
standardise SNe Ia in cosmological applications. This has implications for the
cosmological fitting of SN Ia light curves.Comment: 19 pages, 19 figures, accepted for publication in MNRA
Synthesis and stereoselective oxidation of α-Thio-β- chloropropenyloxazolidin-2-ones
Investigation of the stereoselective reaction of α-thiopropanoyloxazolidin-2-ones with NCS to yield α-thio-β-chloropropenyloxazolidin-2-ones is described. Diastereoselective sulfur oxidation of the resulting α-thio-β-chloropropenyloxazolidin-2-ones is also discussed, with
modest diastereocontrol achieved. However, through a combination of diastereoselective oxidation and subsequent kinetic resolution in the sulfoxide oxidation, diastereoselectivities of up to 94% de are achieved
- …