Catalytic Enantioselective Reactions from Research to Application. Diarylmethanol-Containing Auxiliaries as a Study Case

Chiral auxiliaries – in the broadest possible definition of the term – can be obtained by Grignard reactions of Aryl-MgX with chiral esters R*CO2R. The products formed all contain a diarylmethanol structural moiety. They can be used in stoichiometric and catalytic enantioselective reactions, preferably as ligands on metal centers. They have also found applications for enantioselective inclusions, for solid-phase reactions, and for liquid-crystal preparations

6-Chloromethylierte 2-(tert-Butyl)-1,3-dioxan- und -1,3-dioxin-4-one aus (R)- oder (S)-4,4,4- Trichloro-3- hydroxybuttersaure

Enantiopure (2S,6R)-and (2R,6S)-2-(tert-butyl)-1,3-dioxan-3-ones (2 and 3, resp., cis-configuration) are prepared from each of the commercially available enantiomeric 4,4,4-trichloro-3-hydroxybutanoic acids and pivalaldehyde (52%, after crystallization). Bromination of 2 with NBS in CCl4 gives an unstable bromo-trichloro-dioxanone to which structure D is tentatively assigned. Passing a solution of the crude product D in Et2O through a column of acidic Al2O3, (S)-6-(bromodichloromethyl)-2-(tert-butyl)-1,3-dioxin-4-one (7) is formed (ca, 70% overall yield from 2 on a 50-mmol scale). Treatment of the crude D with Zn powder in Et2O leads to (S)-2-(tert-butyl)-6-(dichloromethyl)-1,3-dioxin-4-one (9, ca. 35% from 2 on a 20-mmol scale). Reductive dehalogenations of 2 and 7 with triphenyltin hydride can be carried out selectively to produce the (dichloromethyl)- and (chloromethyl)-dioxanones 5 and 6, resp., and the (dichloromethyl)-, (chloromethyl)-, and non-chlorinated dioxinones 9, 10, and 11, resp. (yields after distillation and chromatography 37–49%)

High Resolution X-Ray Imaging of the Center of IC342

We presented the result of a high resolution (FWHM~0.5'') 12 ks Chandra HRC-I observation of the starburst galaxy IC342 taken on 2 April 2006. We identified 23 X-ray sources within the central 30' x 30' region of IC342. Our HRC-I observation resolved the historical Ultraluminous X-ray sources (ULX), X3, near the nucleus into 2 sources, namely C12 and C13, for the first time. The brighter source C12, with L(0.08-10keV)=(6.66\pm0.45)\times10^{38}ergs^-1, was spatially extended (~82 pc x 127 pc). From the astrometric registration of the X-ray image, C12 was at R.A.=03h:46m:48.43s, decl.=+68d05m47.45s, and was closer to the nucleus than C13. Thus we concluded that source was not an ULX and must instead be associated with the nucleus. The fainter source C13, with L(0.08-10keV)=(5.1\pm1.4) x 10^{37}ergs^-1 was consistent with a point source and located $6.51'' at P.A. 240 degree of C12. We also analyzed astrometrically corrected optical Hubble Space Telescope and radio Very Large Array images, a comparison with the X-ray image showed similarities in their morphologies. Regions of star formation within the central region of IC342 were clearly visible in HST H alpha image and this was the region where 3 optical star clusters and correspondingly our detected X-ray source C12 were observed. We found that a predicted X-ray emission from starburst was very close to the observed X-ray luminosity of C12, suggesting that nuclear X-ray emission in IC342 was dominated by starburst. Furthermore, we discussed the possibility of AGN in the nucleus of IC342. Although our data was not enough to give a firm existence of an AGN, it could not be discarded.Comment: 29 page, 8 figures, accepted by Ap

Reduction of Ketones with LiAlH4 Complexes of α,α,α\u27,α\u27-Tetraaryl-1,3-dioxolane-4,5-dimethanols (TADDOLs) A Combination of Enantioselective Reduction and Clathrate Formation with a Discussion of LAH Reagents Bearing C2-Symmetrical Ligands

A complex prepared from one equivalent each of LiAlH4, EtOH and a TADDOL (α,α,α\u27,α\u27-tetraaryl-1,3-dioxolane-4,5-dimethanol) reduces aryl alkyl ketones to sec. alcohols with enantiomer ratios (er) up to 96 : 4. The chiral LAH derivative is used in two-fold excess in THF solution and at dry ice temperatures. The ability of TADDOLs to form clathrates diastereoselectively can be exploited to increase the er of the initially formed alcohols by a simple modification of the work-up procedure and hence, products of very high en- antiopurity (er 99 : 1) can be isolated. When (7i,/i)-TADDOLs (from (ZiA)-tartrate) are applied in the reaction, the 1-aryl-alkanols formed preferentially have (S) configuration, as for the products obtained with the corresponding (P)-BINOL and (P)-BIPHENOL derivatives. A common mechanistic model is discussed

Grossansätze zur Herstellung von α,α,α',α'-Tetraaryl-1,3-dioxolan-4,5-dimethanolen (TADDOLe): Nützliche Hilfsstoffe für die EPC-Synthese und ihre Struktur im Festkörper

The large-scale preparation of α,α,α',α'-tetraaryl-1,3-dioxolan-4,5-dimethanol derivatives is described. It consists of acetalization of dimethyl tartrate and Grignard addition. The diols 2–12 thus obtained are crystalline and stable. They are useful as versatile auxiliaries for enantioselective reactions and for resolutions by clathrate formation. The X-ray crystal structure of the inclusion compound from one of the TADDOLs and CCl4 is described (6·2 CCl4) and compared with the structures of analogous derivatives, including C2-symmetrical diphosphines. Reference is given to other chiral auxiliaries containing the diaryl-methanol group

Consequences of temperature fluctuations in observables measured in high energy collisions

We review the consequences of intrinsic, nonstatistical temperature fluctuations as seen in observables measured in high energy collisions. We do this from the point of view of nonextensive statistics and Tsallis distributions. Particular attention is paid to multiplicity fluctuations as a first consequence of temperature fluctuations, to the equivalence of temperature and volume fluctuations, to the generalized thermodynamic fluctuations relations allowing us to compare fluctuations observed in different parts of phase space, and to the problem of the relation between Tsallis entropy and Tsallis distributions. We also discuss the possible influence of conservation laws on these distributions and provide some examples of how one can get them without considering temperature fluctuations.Comment: Revised version of the invited contribution to The European Physical Journal A (Hadrons and Nuclei) topical issue about 'Relativistic Hydro- and Thermodynamics in Nuclear Physics' guest eds. Tamas S. Biro, Gergely G. Barnafoldi and Peter Va

Prognostic implications of the Quebec Task Force classification of back-related leg pain: An analysis of longitudinal routine clinical data

Background: Low back pain (LBP) patients with related leg pain have a more severe profile than those with local LBP and a worse prognosis. Pain location above or below the knee and the presence of neurological signs differentiate patients with different profiles, but knowledge about the prognostic value of these subgroups is sparse. The objectives of this study were (1) to investigate whether subgroups consisting of patients with Local LBP only, LBP + leg pain above the knee, LBP + leg pain below the knee, and LBP + leg pain and neurological signs had different prognoses, and (2) to determine if this was explained by measured baseline factors. Methods. Routine clinical data were collected during the first visit to an outpatient department and follow-ups were performed after 3 and 12 months. Patients were divided into the four subgroups and associations between subgroups and the outcomes of activity limitation, global perceived effect (GPE) after 3 months, and sick leave after 3 months were tested by means of generalised estimating equations. Models were univariate (I), adjusted for duration (II), and adjusted for all baseline differences (III). Results: A total of 1,752 patients were included, with a 76% 3-month and 70% 12-month follow-up. Subgroups were associated with activity limitation in all models (p < 0.001). Local LBP had the least and LBP + neurological signs the most severe limitations at all time-points, although patients with neurological signs improved the most. Associations with GPE after 3 months were only significant in Model I. Subgroups were associated with sick leave after 3 months in model I and II, with sick leave being most frequent in the subgroup with neurological signs. No significant differences were found in any pairwise comparisons of patients with leg pain above or below the knee. Conclusions: Subgrouping LBP patients, based on pain location and neurological signs, was associated with activity limitation and sick leave, but not with GPE. The presence of neurological signs and pain in the leg both have prognostic implications but whether that leg pain without neurological signs is above or below the knee does not