Iron(II)-Catalyzed 1,2-Diamination of Styrenes Installing a Terminal NH2 Group Alongside Unprotected Amines.

1,2-Diamination of alkenes represents an attractive way to generate differentiated vicinal diamines, which are prevalent motifs in biologically active compounds and catalysts. However, existing methods are usually limited in scope and produce diamines where one or both nitrogens are protected, adding synthetic steps for deprotection and further N-functionalization to reach a desired target. Furthermore, the range of amino groups that can be introduced at the internal position is fairly limited. Here we describe a 1,2-diamination of styrenes that directly installs a free amino group at the terminal position and a wide variety of unprotected nitrogen nucleophiles (primary or secondary alkyl or aromatic amines, sulfoximines, N-heterocycles, and ammonia surrogate) at the internal position. Two complementary sets of conditions encompass electronically activated and deactivated styrenes with diverse substitution patterns and functional groups. Moreover, this strategy can be extended to the 1,2-aminothiolation of styrenes.

Wide Critical Fluctuations of the Field-Induced Phase Transition in Graphite.

In the immediate vicinity of the critical temperature (T_{c}) of a phase transition, there are fluctuations of the order parameter that reside beyond the mean-field approximation. Such critical fluctuations usually occur in a very narrow temperature window in contrast to Gaussian fluctuations. Here, we report on a study of specific heat in graphite subject to a high magnetic field when all carriers are confined in the lowest Landau levels. The observation of a BCS-like specific heat jump in both temperature and field sweeps establishes that the phase transition discovered decades ago in graphite is of the second order. The jump is preceded by a steady field-induced enhancement of the electronic specific heat. A modest (20%) reduction in the amplitude of the magnetic field (from 33 to 27 T) leads to a threefold decrease of T_{c} and a drastic widening of the specific heat anomaly, which acquires a tail spreading to two times T_{c}. We argue that the steady departure from the mean-field BCS behavior is the consequence of an exceptionally large Ginzburg number in this dilute metal, which grows steadily as the field lowers. Our fit of the critical fluctuations indicates that they belong to the 3DXY universality class as in the case of the ^{4}He superfluid transition.

Calcium-Catalyzed Synthesis of Polysubstituted 2-Alkenylfurans from ß-Keto Esters Tethered to Propargyl Alcohols.

An efficient synthesis of polysubstituted 2-alkenylfurans using Ca(NTf2 )2 /KPF6 as a catalytic mixture is described. It is based on the cycloelimination of readily available propargyl alcohols tethered to ß-keto esters under dry conditions to avoid competitive Meyer-Schuster rearrangement. The furan can be further functionalized in situ by a calcium-catalyzed Friedel-Crafts-type reaction with secondary and tertiary alcohols. The title reaction allows for the high-yielding preparation of di-, tri-, and tetrasubstituted 2-alkenylfurans, which are important subunits of bioactive compounds.

Broken rotational symmetry in the pseudogap phase of a high-T(c) superconductor.

The nature of the pseudogap phase is a central problem in the effort to understand the high-transition-temperature (high-T(c)) copper oxide superconductors. A fundamental question is what symmetries are broken when the pseudogap phase sets in, which occurs when the temperature decreases below a value T*. There is evidence from measurements of both polarized neutron diffraction and the polar Kerr effect that time-reversal symmetry is broken, but at temperatures that differ significantly from one another. Broken rotational symmetry was detected from both resistivity measurements and inelastic neutron scattering at low doping, and from scanning tunnelling spectroscopy at low temperature, but showed no clear relation to T*. Here we report the observation of a large in-plane anisotropy of the Nernst effect in YBa(2)Cu(3)O(y) that sets in precisely at T* throughout the doping phase diagram. We show that the CuO chains of the orthorhombic lattice are not responsible for this anisotropy, which is therefore an intrinsic property of the CuO(2) planes. We conclude that the pseudogap phase is an electronic state that strongly breaks four-fold rotational symmetry. This narrows the range of possible states considerably, pointing to stripe or nematic order.

Ca(II) -catalyzed alkenylation of alcohols with vinylboronic acids.

Direct alkenylation of a variety of alcohols with vinylboronic acids has been accomplished using the air-stable calcium(II) complex Ca(NTf2 )2 under mild conditions with short reaction times. For reluctant transformations, an ammonium salt was used as an additive to circumvent the reactivity issue.

Enhancement of the Nernst effect by stripe order in a high-T(c) superconductor.

The Nernst effect in metals is highly sensitive to two kinds of phase transition: superconductivity and density-wave order. The large, positive Nernst signal observed in hole-doped high-T(c) superconductors above their transition temperature (T(c)) has so far been attributed to fluctuating superconductivity. Here we report that in some of these materials the large Nernst signal is in fact the result of stripe order, a form of spin/charge modulation that causes a reconstruction of the Fermi surface. In La(2-x)Sr(x)CuO(4) (LSCO) doped with Nd or Eu, the onset of stripe order causes the Nernst signal to change from being small and negative to being large and positive, as revealed either by lowering the hole concentration across the quantum critical point in Nd-doped LSCO (refs 6-8) or by lowering the temperature across the ordering temperature in Eu-doped LSCO (refs 9, 10). In the second case, two separate peaks are resolved, respectively associated with the onset of stripe order at high temperature and superconductivity near T(c).

Two phase transitions induced by a magnetic field in graphite.

Different instabilities have been speculated for a three-dimensional electron gas confined to its lowest Landau level. The phase transition induced in graphite by a strong magnetic field, and believed to be a charge density wave, is the only experimentally established case of such instabilities. Studying the magnetoresistance in graphite for the first time up to 80 T, we find that the magnetic field induces two successive phase transitions, consisting of two distinct ordered states each restricted to a finite field window. In both states, an energy gap opens up in the out-of-plane conductivity and coexists with an unexpected in-plane metallicity for a fully gap bulk system. Such peculiar metallicity may arise as a consequence of edge-state transport expected to develop in the presence of a bulk gap.

Quantum oscillations and the Fermi surface in an underdoped high-Tc superconductor.

Despite twenty years of research, the phase diagram of high-transition-temperature superconductors remains enigmatic. A central issue is the origin of the differences in the physical properties of these copper oxides doped to opposite sides of the superconducting region. In the overdoped regime, the material behaves as a reasonably conventional metal, with a large Fermi surface. The underdoped regime, however, is highly anomalous and appears to have no coherent Fermi surface, but only disconnected 'Fermi arcs'. The fundamental question, then, is whether underdoped copper oxides have a Fermi surface, and if so, whether it is topologically different from that seen in the overdoped regime. Here we report the observation of quantum oscillations in the electrical resistance of the oxygen-ordered copper oxide YBa2Cu3O6.5, establishing the existence of a well-defined Fermi surface in the ground state of underdoped copper oxides, once superconductivity is suppressed by a magnetic field. The low oscillation frequency reveals a Fermi surface made of small pockets, in contrast to the large cylinder characteristic of the overdoped regime. Two possible interpretations are discussed: either a small pocket is part of the band structure specific to YBa2Cu3O6.5 or small pockets arise from a topological change at a critical point in the phase diagram. Our understanding of high-transition-temperature (high-T(c)) superconductors will depend critically on which of these two interpretations proves to be correct.

Electron pockets in the Fermi surface of hole-doped high-Tc superconductors.

High-temperature superconductivity in copper oxides occurs when the materials are chemically tuned to have a carrier concentration intermediate between their metallic state at high doping and their insulating state at zero doping. The underlying evolution of the electron system in the absence of superconductivity is still unclear, and a question of central importance is whether it involves any intermediate phase with broken symmetry. The Fermi surface of the electronic states in the underdoped 'YBCO' materials YBa2Cu3O(y) and YBa2Cu4O8 was recently shown to include small pockets, in contrast with the large cylinder that characterizes the overdoped regime, pointing to a topological change in the Fermi surface. Here we report the observation of a negative Hall resistance in the magnetic-field-induced normal state of YBa2Cu3O(y) and YBa2Cu4O8, which reveals that these pockets are electron-like rather than hole-like. We propose that these electron pockets most probably arise from a reconstruction of the Fermi surface caused by the onset of a density-wave phase, as is thought to occur in the electron-doped copper oxides near the onset of antiferromagnetic order. Comparison with materials of the La2CuO4 family that exhibit spin/charge density-wave order suggests that a Fermi surface reconstruction also occurs in those materials, pointing to a generic property of high-transition-temperature (T(c)) superconductors.

Nernst and Seebeck coefficients of the cuprate superconductor YBa2Cu3O6.67: a study of Fermi surface reconstruction.

The Seebeck and Nernst coefficients S and nu of the cuprate superconductor YBa{2}Cu{3}O{y} (YBCO) were measured in a single crystal with doping p=0.12 in magnetic fields up to H=28 T. Down to T=9 K, nu becomes independent of field by H approximately 30 T, showing that superconducting fluctuations have become negligible. In this field-induced normal state, S/T and nu/T are both large and negative in the T-->0 limit, with the magnitude and sign of S/T consistent with the small electronlike Fermi surface pocket detected previously by quantum oscillations and the Hall effect. The change of sign in S(T) at T approximately 50 K is remarkably similar to that observed in La2-xBaxCuO4, La{2-x-y}Nd{y}Sr_{x}CuO{4}, and La{2-x-y}Eu{y}Sr{x}CuO{4}, where it is clearly associated with the onset of stripe order. We propose that a similar density-wave mechanism causes the Fermi surface reconstruction in YBCO.

Cobalt-mediated linear 2:1 co-oligomerization of alkynes with enol ethers to give 1-alkoxy-1,3,5-trienes: a missing mode of reactivity.

A variety of 1,6-heptadiynes and certain borylalkynes co-oligomerize with enol ethers in the presence of [CpCo(C(2)H(4))(2)] (Cp=cyclopentadienyl) to furnish the hitherto elusive acyclic 2:1 products, 1,3,5-trien-1-ol ethers, in preference to or in competition with the alternative pathway that leads to the standard [2+2+2] cycloadducts, 5-alkoxy-1,3-cyclohexadienes. Minor variations, such as lengthening the diyne tether, cause reversion to the standard mechanism. The trienes, including synthetically potent borylated derivatives, are generated with excellent levels of chemo-, regio-, and diastereoselectivity, and are obtained directly by decomplexation of the crude mixtures during chromatography. The cyclohexadienes are isolated as the corresponding dehydroalkoxylated arenes. In one example, even ethene functions as a linear cotrimerization partner. The alkoxytrienes are thermally labile with respect to 6pi-electrocyclization-elimination to give the same arenes that are the products of cycloaddition. The latter, regardless of the mechanism of their formation, can be viewed as the result of a formal [2+2+2] cyclization of the starting alkynes with acetylene. One-pot conditions for the exclusive formation of arenes are developed. DFT computations indicate that cyclohexadiene and triene formation share a common intermediate, a cobaltacycloheptadiene, from which reductive elimination and beta-hydride elimination compete.

Quantum-dot assisted spectroscopy of degeneracy-lifted Landau levels in graphene.

Energy spectroscopy of strongly interacting phases requires probes which minimize screening while retaining spectral resolution and local sensitivity. Here, we demonstrate that such probes can be realized using atomic sized quantum dots bound to defects in hexagonal Boron Nitride tunnel barriers, placed at nanometric distance from graphene. With dot energies capacitively tuned by a planar graphite electrode, dot-assisted tunneling becomes highly sensitive to the graphene excitation spectrum. The spectra track the onset of degeneracy lifting with magnetic field at the ground state, and at unoccupied excited states, revealing symmetry-broken gaps which develop steeply with magnetic field - corresponding to Landé g factors as high as 160. Measured up to B = 33 T, spectra exhibit a primary energy split between spin-polarized excited states, and a secondary spin-dependent valley-split. Our results show that defect dots probe the spectra while minimizing local screening, and are thus exceptionally sensitive to interacting states.

Synthesis of tricyclic fused 3-aminopyridines through intramolecular Co(I)-catalyzed [2+2+2] cycloaddition between ynamides, nitriles, and alkynes.

Three-ring circus: An expedient route to tricyclic fused 2-trimethylsilyl-3-aminopyridines exhibiting unprecedented skeletons is described. The key step is a very efficient cobalt-catalyzed [2+2+2] cycloaddition of a polyunsaturated compound displaying an ynamide, an alkyne, and a nitrile functionality (see picture). The first [2+2+2] cocyclizations between ynamides, nitriles, and alkynes are reported. They open a new access to unprecedented nitrogen-containing heterocycles of type 2-trimethylsilyl-3-aminopyridines. Such frameworks, which can be found in various compounds of biological interest, are very difficult to prepare by conventional methods. However, using [CpCo(C(2)H(4))(2)] (Cp=cyclopentadienyl) as catalyst, the intramolecular cyclizations could be achieved in up to 100 % yield. The presence of the trimethylsilyl group allowed a rare type of Hiyama cross-coupling: one of the silylated pyridines could be coupled with p-iodoanisole to give a new type of biaryl system.

Gold(I)-catalyzed macrocyclization of 1,n-enynes.

The gold(I)-catalyzed [2 + 2] cycloaddition of large 1,n-enynes (n = 10-16) provides access to 9- to 15-membered ring macrocycles incorporating a cyclobutene moiety. The reaction requires the use of a gold(I) catalyst bearing a sterically hindered biphenylphosphine ligand.

Access to the protoilludane core by gold-catalyzed allene-vinylcyclopropane cycloisomerization.

Gold(I)-catalyzed allene-vinylcyclopropane cycloisomerization leads to the tricyclic framework of the protoilludanes in a single step by a reaction that involves a cyclopropane ring expansion and a Prins cyclization.

Cobalt(I)-mediated preparation of polyborylated cyclohexadienes: scope, limitations, and mechanistic insight.

A series of 1,3- and 1,4-diboryl-1,3-cyclohexadienes have been prepared by intermolecular CoCp-mediated [2+2+2] cocyclizations of alkynylboronic pinacolate esters with alkenes, followed by oxidative demetallation with iron(III) chloride. The effect of substitution at the borylated alkyne on chemo- and regioselectivities has been studied, suggesting steric control. The proper choice of substituents allowed the preparation of 1,3-diborylated cyclohexadienes in a highly selective manner. Alternatively, 1,4-diborylated cyclohexadienes could be prepared from diborylated diynes. The scope of this reaction has been examined and found to include electron-poor, electron-rich, linear, and cyclic alkenes. The diborylated cyclohexadienes were submitted to single or double Suzuki-Miyaura cross-coupling reactions with haloarenes to afford polyarylated systems. The mechanism of the title reaction, including the regioselectivity of the cycloaddition steps, has been analyzed by means of DFT computations.

Molecular bond formation between surfaces: anchoring and shearing effects.

Specific molecular bonds between apposing surfaces play a central role in many biological structures and functions. They display a widely varying anchoring to the cell surface, and they are subject to forces that affect their binding characteristics due to their hydrodynamic environments. Here, we examine both anchoring and shearing aspects using simplified model systems aimed at gaining insight into the formation of a 2D bond collection under stress using two different surface anchors. The highly specific streptavidin-biotin molecular bond was chosen as the model receptor-ligand pair, and grafted colloids were used as model surfaces. To explore the role of the surface anchor, we grafted biotin onto the particle surface following two different approaches: first, the grafting was performed directly on the particle amine functions; second, a 35-nm-long PEG spacer was used. Hybrid particle classes were brought into contact in a homogeneous shear (between 200 s(-)(1) and 1200 s(-)(1)) using a cone plate geometry. The bond association and dissociation kinetics were given by the time course assemblage of hybrid particles into doublets. We observed saturating kinetics profiles that we interpreted as a linkage-breakage equilibrium, which yielded the on and off rates. We found that the biotin-PEG spacer was needed in order to observe significant binding at any shear rate. We also showed that only the number of collisions per unit time, generated by the shear, affected the on rate of the binding. Neither the exerted forces nor the collision lifetime had any effect. The off rate decreased with shear, possibly because of the shortening of the force duration, which results from the increasing shear rate.