Lewis acid platinum complexes of conformationally flexible NUPHOS diphosphines: Highly efficient catalysts for the carbonyl-ene reaction

Enantiopure Lewis acid complexes of conformationally flexible acyclic and monocyclic NUPHOS diphosphines, delta- and lambda-[(NUPHOS)Pt(OTf)(2)], are efficient catalysts for the carbonyl-ene reaction between various unsymmetrical 1,1'-disubstituted alkenes and phenylglyoxal or ethyl glyoxylate. While catalyst performance was substrate dependent, ee values as high as 95% and yields up to 90% have been obtained. In a number of cases catalysts generated from delta- and lambda-[(NUPHOS)Pt{(S)-BINOL}] showed marked enhancements in enantioselectivity in ionic liquids compared with organic media. Although an enhancement in enantioselectivity was not obtained for all substrate combinations in such cases, the enantioselectivities were comparable to those obtained in dichloromethane. Furthermore, although the ee's are initially comparable in both the ionic liquid and dichloromethane, a gradual erosion of ee with time was found in the organic solvent, whereas the ee remained constant in the ionic liquid. Preliminary kinetic investigations suggest that the decrease in ee may be due to a faster racemization of the catalyst in dichloromethane compared with the ionic liquid.

Comparative study of diastereoisomer interconversion in chiral BINOL-ate and diamine platinum complexes of conformationally flexible NUPHOS diphosphines

A thorough and detailed study of diastereointerconversion in the chiral platinum complexes [(NUPHOS)Pt{(S)-BINOL}] (3a-e) has been undertaken and compared with the results of a similar study with [(BIPHEP)Pt{(S)-BINOL}]. Rate data revealed that this process obeys first-order relaxation kinetics, and rate constants for conversion of the minor to the major diastereoisomer have been obtained. Eyring analysis of the data gave DeltaH(double dagger) and DeltaS(double dagger) values of 22-25 kcal mol(-1) and -1 to -16 eu, respectively. In combination with computational analysis, these studies indicate that atropinversion most likely occurs via an on-metal pathway involving a planar seven-membered transition state. Substitution of (S)-BINOL for (S,S)-DPEN results in a marked reduction in the barrier to atropinversion; a DeltaH(double dagger) value of 17 kcal mol(-1) has been determined for the conversion of delta-[(Ph-4-NUPHOS)Pt{(S,S)-DPEN}]Cl-2 to lambda-[(Ph-4-NUPHOS)Pt{(S,S)-DPEN}]Cl-2, which could indicate that an alternative mechanism operates.

Highly efficient asymmetric hetero-Diels-Alder reactions of carbonyl compounds catalyzed by Lewis acid platinum complexes of conformationally flexible NUPHOS-type diphosphines

Conformationally flexible NUPHOS-type diphosphines have been resolved as their diastereopure platinum BINOLate complexes delta- and lambda-[(NUPHOS)Pt{(S)-BINOL}] and the corresponding enantiopure Lewis acids delta- and lambda-[(NUPHOS)Pt(OTf)(2)], being generated by protonation with trifluoromethanesulfonic acid, act as highly efficient catalysts for the hetero-Diels-Alder reaction of nonactivated conjugated dienes with aryl glyoxals and glyoxylate esters, giving ee's as high as 99%.

Determination of absolute configuration of conformationally flexible cis-dihydrodiol metabolites: Effect of diene substitution pattern on the circular dichroism spectra and optical rotations

Absolute configurations of a number of cis-dihydrodiols (cis-1,2-dihydroxy-3,5-cyclohexadienes), synthetically useful products of TDO-catalyzed dihydroxylations of 1,2- and 1,3-disubstituted benzene derivatives, have been determined by a comparison of calculated and experimental CD spectra and optical rotations and by methods involving X-ray crystallography, H-1 NMR spectra of diastereoisomeric derivatives, and by stereochemical correlations. The computations disclosed a significant effect of the substituents on conformational equilibria of cis-dihydrodiols and chiroptical properties of individual conformers. The assigned absolute configurations of cis-dihydrodiols have allowed the validity of a simple predictive model for TDO-catalyzed arene dihydroxylations to be extended.

Absolute configuration of conformationally flexible cis-dihydrodiol metabolites by the method of confrontation of experimental and calculated electronic CD spectra and optical rotations

We have determined the absolute configurations of conformationally flexible cis-dihydrodiol metabolites (cis-1,2-dihydroxy-3,5-cyclohexadienes), bearing different substituents (e.g., Br, F, CF3, CN, Me) in 3- and 5-positions, by the method of confrontation of experimental and calculated electronic CD spectra and optical rotations. Convergent results were obtained by both methods in eight out of ten cases. For the difficult cases, where either conformer population and/or chiroptical properties (calculated rotational strengths of the long-wavelength Cotton effect or optical rotations) of contributing conformers remain inconclusive, the absolute configuration could still be correctly assigned based on one of the biased properties (either ECD or optical rotation). This approach appears well-suited for a broad spectrum of conformationally flexible chiral molecules.

After the Male Breadwinner Model? Childcare Services and the Division of Labor in European Countries

Fundamental reforms in childcare services appear to have eroded traditional
support to the male breadwinner model across European states. There has been a strong debate about the direction of these changes, and the ways in which childcare services can alter the division of labor and promote gender equality. This paper deals with these issues by using fuzzy set ideal-type analysis to assess the conformity of childcare service provisions in European economies to Fraser’s four ideal typical models: male breadwinner, caregiver parity, universal breadwinner, and universal caregiver. We find that there is resilience of traditional gender roles in the majority of European countries, while there are different variants of the universal breadwinner shaping different forms of childcare policies. The more equalitarian universal caregiver model maintains its utopian character.

Difficult Labor: Troublesome Company at the New Birth of Freedom

Extended contribution to a roundtable on Mark A. Lause's Free Labor: The Civil War and the Making of an American Working Class, emphasizing the wartime labor movement's great difficulty in responding to rapid industrialization brought on by the war, and to the increasing diversity of the labor force brought about by mass immigration.

Searching for the IRA 'disappeared': Ground-penetrating radar investigation of a churchyard burial site, Northern Ireland

A search for the body of a victim of terrorist abduction and murder was made in a graveyard on the periphery of a major conurbation in Northern Ireland. The area is politically sensitive and the case of high profile. This required non-invasive, completely non-destructive and rapid assessment of the scene. A MALA RAMAC ground-penetrating radar system was used to achieve these objectives. Unprocessed and processed 400MHz data shows the presence of a collapse feature above and around a known 1970s burial with no similar collapse above the suspect location. In the saturated, clay-rich sediments of the site, 200MHz data offered no advantage over 400MHz data. Unprocessed 100MHz data shows a series of multiples in the known burial with no similar features in the suspect location. Processed 100MHz lines defined the shape of the collapse around the known burial to 2m depth, together with the geometry of the platform (1m depth) the gravedigger used in the 1970s to construct the site. In addition, processed 100MHz data showed both the dielectric contrast in and internal reflection geometry of the soil imported above the known grave. Thus the sequence, geometry, difference in infill and infill direction of the grave was reconstructed 30 years after burial. The suspect site showed no evidence of shallow or deep inhumation. Subsequently, the missing person������¢���¯���¿���½���¯���¿���½s body was found some distance from this site, vindicating the results and interpretation from ground-penetrating radar. The acquisition, processing, collapse feature and sequence stratigraphic interpretation of the known burial and empty (suspect) burial site may be useful proxies for other, similar investigations. GPR was used to evaluate this site within 3 hours of the survey commencing, using unprocessed data. An additional day of processing established that the suspect body did not reside here, which was counter to police and community intelligence.

The Mixed Fortunes of Irish Unions: Living with the Paradoxes of Social Partnership

We assess the fortunes of Irish unions since 1980 and, in particular, focus on the period of national social partnership since 1987. We argue that, structurally, unions have been weakened by a sharp decline in union density levels. In addition, labor law reform has not been as permissive as unions desired. However, on the other hand, we highlight that union membership in Ireland has never been higher and unions exert a strong influence over many areas of government policy. In conclusion, we argue that continuing with social partnership is the most viable option for Irish unions, though significant gains in union power are unlikely to happen.

Description and search labor for information retrieval

Selection power is taken as the fundamental value for information retrieval systems. Selection power is regarded as produced by selection labor, which itself separates historically into description and search labor. As forms of mental labor, description and search labor participate in the conditions for labor and for mental labor. Concepts and distinctions applicable to physical and mental labor are indicated, introducing the necessity of labor for survival, the idea of technology as a human construction, and the possibility of the transfer of human labor to technology. Distinctions specific to mental labor, particular between semantic and syntactic labor, are introduced. Description labor is exemplified by cataloging, classification, and database description, can be more formally understood as the labor involved in the transformation of objects for description into searchable descriptions, and is also understood to include interpretation. The costs of description labor are discussed. Search labor is conceived as the labor expended in searching systems. For both description and search labor, there has been a progressive reduction in direct human labor, with its syntactic aspects transferred to technology, effectively compelled by the high relative costs of direct human labor compared to machine processes.