Synthesis of bench-stable solid triorganoindium reagents and reactivity in palladium-catalyzed cross-coupling reactions

[Abstract] Bench-stable solid triorganoindium compounds have been prepared by coordination with 4-(dimethylamino)pyridine (DMAP). The solid R3In(DMAP) complexes are obtained from the corresponding solution of R3In in quantitative yield and can be stored for up to several weeks. These reagents show excellent reactivity in palladium-catalyzed cross-coupling reactions with organic electrophiles.Ministerio de Economía y Competitividad; CTQ2015-68369-PGalicia. Consellería de Cultura, Educación e Ordenación Universitaria; GRC2014/04

Transition-metal-free cross-coupling of indium organometallics with chromene and isochroman acetals mediated by BF3·OEt2

[Abstract] A transition-metal-free coupling of triorganoindium reagents with benzopyranyl acetals mediated by a Lewis acid has been developed. The reaction of R3In with chromene and isochroman acetals in the presence of BF3·OEt2 afforded 2-substituted chromenes and 1-substituted isochromans, respectively, in good yields. The reactions proceed with a variety of triorganoindium reagents (aryl, heteroaryl, alkynyl, alkenyl, alkyl) using only 50 mol % of the organometallic, thus demonstrating the efficiency of these species. Preliminary mechanistic studies indicate the formation of an oxocarbenium ion intermediate in the presence of the Lewis acid.Ministerio de Economía y Competitividad; CTQ2012-31200Ministerio de Economía y Competitividad; CTQ2015-68369-

The Institute for the History of Rheumatology, an offspring of the Italian Society of Rheumatology, is born in Venice.

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Bypass urbanism: Re-ordering center-periphery relations in Kolkata, Lagos and Mexico City

This paper introduces the concept of “bypass urbanism” to account for a process of urbanization that is reordering center-periphery relations of urban regions into new hierarchies. Bypass urbanism became visible through a comparison of large-scale urban transformations at the peripheries of Kolkata, Lagos, and Mexico City by zooming out and considering their impacts on the socio-spatial structure of the extended urban regions. Bypass urbanism is not emerging from the construction of a singular new town or real estate project, but is the result of the simultaneous development of an ensemble of various independent but related projects. Therefore, bypass urbanism usually does not emanate from a coherent planning initiative, even less so from a hidden “master plan” at the hands of any single developer or state agency, but it emerges through a convergence of interests over large areas of land at the geographical periphery of urban regions that have been made available for new urban developments by various measures. We understand bypass urbanism as a multidimensional process that includes material-geographical bypassing, the bypassing of regulatory frameworks, and socio-economic bypassing in everyday life. It results in the creation of exclusive and excluding spaces that enable middle and upper-class lifestyles, at the same time leading to the peripheralization of extant urban areas that are bypassed and neglected. The massive scale of bypass urbanism that we have observed represents a new quality of urban development resulting not in isolated urban enclaves or archipelagos, but in the fundamental restructuring of the extended urban region with far reaching and incalculable repercussions

Constraints on the χ_(c1) versus χ_(c2) polarizations in proton-proton collisions at √s = 8 TeV

The polarizations of promptly produced χ_(c1) and χ_(c2) mesons are studied using data collected by the CMS experiment at the LHC, in proton-proton collisions at √s=8  TeV. The χ_c states are reconstructed via their radiative decays χ_c → J/ψγ, with the photons being measured through conversions to e⁺e⁻, which allows the two states to be well resolved. The polarizations are measured in the helicity frame, through the analysis of the χ_(c2) to χ_(c1) yield ratio as a function of the polar or azimuthal angle of the positive muon emitted in the J/ψ → μ⁺μ⁻ decay, in three bins of J/ψ transverse momentum. While no differences are seen between the two states in terms of azimuthal decay angle distributions, they are observed to have significantly different polar anisotropies. The measurement favors a scenario where at least one of the two states is strongly polarized along the helicity quantization axis, in agreement with nonrelativistic quantum chromodynamics predictions. This is the first measurement of significantly polarized quarkonia produced at high transverse momentum