3,4-and 3,5-disubstituted 2-pyridones using an intermolecular cycloaddition/cycloreversion strategy: toward the synthesis of aristopyridinone A

The intermolecular cycloaddition of pyrazinone precursors with alkyne substrates was evaluated. The resulting regioisomeric [2.2.2]-diketopiperazine alkene cycloadducts were diverted into 2-pyridone products through cycloreversion of the [2.2.2]-bicyclic intermediates. New insights into the regioselectivity of pyrazinone azadiene Diels-Alder reactions as well as cycloreversion reactivity were revealed in this study. Synthetic sequences using this [4+2]/r[4+2] strategy were determined that can produce predominantly the 3,5-disubstituted 2-pyridone alkaloid structures; pyridones featuring the 3,4-substitution pattern are observed as the minor regioisomeric products. (C) 2015 Elsevier Ltd. All rights reserved

The reduced spaces of a symplectic Lie group action

There exist three main approaches to reduction associated to canonical Lie group actions on a symplectic manifold, namely, foliation reduction, introduced by Cartan, Marsden-Weinstein reduction, and optimal reduction, introduced by the authors. When the action is free, proper, and admits a momentum map these three approaches coincide. The goal of this paper is to study the general case of a symplectic action that does not admit a momentum map and one needs to use its natural generalization, a cylinder valued momentum map introduced by Condevaux, Dazord, and Molino. In this case it will be shown that the three reduced spaces mentioned above do not coincide, in general. More specifically, the Marsden-Weinstein reduced spaces are not symplectic but Poisson and their symplectic leaves are given by the optimal reduced spaces. Foliation reduction produces a symplectic reduced space whose Poisson quotient by a certain Lie group associated to the group of symmetries of the problem equals the Marsden-Weinstein reduced space. We illustrate these constructions with concrete examples, special emphasis being given to the reduction of a magnetic cotangent bundle of a Lie group in the situation when the magnetic term ensures the non-existence of the momentum map for the lifted action. The precise relation of the cylinder valued momentum map with group valued momentum maps for Abelian Lie groups is also given.Comment: 37 page

Mott transition and collective charge pinning in electron doped Sr2IrO4

We studied the in-plane dynamic and static charge conductivity of electron doped Sr2IrO4 using optical spectroscopy and DC transport measurements. The optical conductivity indicates that the pristine material is an indirect semiconductor with a direct Mott-gap of 0.55 eV. Upon substitution of 2% La per formula unit the Mott-gap is suppressed except in a small fraction of the material (15%) where the gap survives, and overall the material remains insulating. Instead of a zero energy mode (or Drude peak) we observe a soft collective mode (SCM) with a broad maximum at 40 meV. Doping to 10% increases the strength of the SCM, and a zero-energy mode occurs together with metallic DC conductivity. Further increase of the La substitution doesn't change the spectral weight integral up to 3 eV. It does however result in a transfer of the SCM spectral weight to the zero-energy mode, with a corresponding reduction of the DC resistivity for all temperatures from 4 to 300 K. The presence of a zero-energy mode signals that at least part of the Fermi surface remains ungapped at low temperatures, whereas the SCM appears to be caused by pinning a collective frozen state involving part of the doped electrons

Collapse of the Mott gap and emergence of a nodal liquid in lightly doped Sr2_2IrO4_4

Superconductivity in underdoped cuprates emerges from an unusual electronic state characterised by nodal quasiparticles and an antinodal pseudogap. The relation between this state and superconductivity is intensely studied but remains controversial. The discrimination between competing theoretical models is hindered by a lack of electronic structure data from related doped Mott insulators. Here we report the doping evolution of the Heisenberg antiferromagnet Sr$_2$IrO$_4$, a close analogue to underdoped cuprates. We demonstrate that metallicity emerges from a rapid collapse of the Mott gap with doping, resulting in lens-like Fermi contours rather than disconnected Fermi arcs as observed in cuprates. Intriguingly though, the emerging electron liquid shows nodal quasiparticles with an antinodal pseudogap and thus bares strong similarities with underdoped cuprates. We conclude that anisotropic pseudogaps are a generic property of two-dimensional doped Mott insulators rather than a unique hallmark of cuprate high-temperature superconductivity

Intermolecular Diels-Alder Cycloaddition for the Construction of Bicyclo[2.2.2]diazaoctane Structures: Formal Synthesis of Brevianamide B and Premalbrancheamide

A stereoselective intermolecular Diels-Alder cycloaddition of an intermediate pyrazinone with both achiral and chiral acrylate-derived dienophiles provides rapid access to the bicyclo[2.2.2]diazaoctane core shared among several prenylated indole alkaloids. The product derived from cydoaddition with 2-nitroacrylate required an additional five to six synthetic operations to intercept established precursors to premalbrancheamide and brevianamide B. The chemistry detailed in this manuscript constitutes a formal total synthesis (12 steps each) of these [2.2.2]diazabicyclic natural products from proline methyl ester

Mott transition and collective charge pinning in electron doped Sr_2IrO_4

We studied the in-plane dynamic and static charge conductivity of electron doped Sr_2IrO_4 using optical spectroscopy and DC transport measurements. The optical conductivity indicates that the pristine material is an indirect semiconductor with a direct Mott gap of 0.55 eV. Upon substitution of 2% La per formula unit the Mott gap is suppressed except in a small fraction of the material (15%) where the gap survives, and overall the material remains insulating. Instead of a zero energy mode (or Drude peak) we observe a soft collective mode (SCM) with a broad maximum at 40 meV. Doping to 10% increases the strength of the SCM, and a zero-energy mode occurs together with metallic DC conductivity. Further increase of the La substitution doesn't change the spectral weight integral up to 3 eV. It does however result in a transfer of the SCM spectral weight to the zero-energy mode, with a corresponding reduction of the DC resistivity for all temperatures from 4 to 300 K. The presence of a zero-energy mode signals that at least part of the Fermi surface remains ungapped at low temperatures, whereas the SCM appears to be caused by pinning a collective frozen state involving part of the doped electrons

Role of structural dynamics at the receptor G protein interface for signal transduction

GPCRs catalyze GDP/GTP exchange in the α-subunit of heterotrimeric G proteins (Gαßγ) through displacement of the Gα C-terminal α5 helix, which directly connects the interface of the active receptor (R*) to the nucleotide binding pocket of G. Hydrogen-deuterium exchange mass spectrometry and kinetic analysis of R* catalysed G protein activation have suggested that displacement of α5 starts from an intermediate GDP bound complex (R*•GGDP). To elucidate the structural basis of receptor-catalysed displacement of α5, we modelled the structure of R*•GGDP. A flexible docking protocol yielded an intermediate R*•GGDP complex, with a similar overall arrangement as in the X-ray structure of the nucleotide free complex (R*•Gempty), however with the α5 C-terminus (GαCT) forming different polar contacts with R*. Starting molecular dynamics simulations of GαCT bound to R* in the intermediate position, we observe a screw-like motion, which restores the specific interactions of α5 with R* in R*•Gempty. The observed rotation of α5 by 60° is in line with experimental data. Reformation of hydrogen bonds, water expulsion and formation of hydrophobic interactions are driving forces of the α5 displacement. We conclude that the identified interactions between R* and G protein define a structural framework in which the α5 displacement promotes direct transmission of the signal from R* to the GDP binding pocket