Synthesis and Properties of 2,3-Diethynyl-1,3-Butadienes

The first general preparative access to compounds of the 2,3-diethynyl-1,3-butadiene (DEBD) class is reported. The synthesis involves a one-pot, twofold Sonogashira-type, Pd⁰-catalyzed coupling of two terminal alkynes and a carbonate derivative of a 2-butyne-1,4-diol. The synthesis is broad in scope and members of this structural family are kinetically stable enough to be handled using standard laboratory techniques at ambient temperature. They decompose primarily through heat-promoted cyclodimerizations, which are impeded by alkyl substitution and accelerated by aryl or alkenyl substitution. An iterative sequence of these unprecedented Sonogashira-type couplings generates a new type of expanded dendralene. A suitably substituted DEBD carrying two terminal alkyne groups undergoes Glaser–Eglinton cyclo-oligomerization to produce a new class of expanded radialenes, which are chiral due to restricted rotation about their 1,3-butadiene units. The structural features giving rise to atropisomerism in these compounds are distinct from those reported previously.     

The bromopentadienyl acrylate approach to himbacine

[reaction: see text] The syntheses of 4,4a-didehydrohimbacine and 4,4a-didehydrohimandravine are presented. Key steps include an intramolecular Diels-Alder reaction of a bromopentadienyl acrylate and Suzuki-Miyaura and Stille coupling reactions.     

Simple Synthetic Receptors for Aspirin

Shallow methylene‐bridged cavitands appended with simple H‐bond donor/acceptor groups are shown to bind aspirin. The structural features needed in a synthetic receptor for aspirin binding are defined.     

Direct Cross‐Couplings of Propargylic Diols

[Pd(PPh₃)₄] catalyzes a Suzuki–Miyaura‐like twofold cross‐coupling sequence between underivatized propargylic diols and either aryl or alkenyl boronic acids to furnish highly substituted 1,3‐dienes. Thus, 2,3‐diaryl‐1,3‐butadienes and their dialkenic congeners ([4]dendralenes) are delivered in a (pseudo)halogen‐free, single‐step synthesis which supersedes existing methods. Allenols are also readily formed. Treatment of these single‐ and twofold cross‐coupled products with acid leads to remarkably short syntheses of highly‐substituted benzofulvenes and aryl indenes, respectively.     

Two new eudesmane derivatives from Verbesina virginica

<正>Two new eudesmane derivatives were isolated from the leaves and flowers of Verbesina virginica,along with the known 6-O-β-E -p-coumaroyl-4α-hydroxyeudesmane(1).Their structures were determined as 6-O-β-Z-p-coumaroyl-4α-hydroxyeudesmane(2) and 6-O-α-E-p-coumaroyl-1β-4α-dihydroxyeudesmane(3) by spectroscopic methods.     

Effect of Pr-Ca substitution on the transport and magnetic behavior of LaMnO3 perovskite

The effect of simultaneous substitution of a fluctuating cation and a divalent cation in LaMnO₃ perovskite modifies the properties of the material to exhibit large valence colossal magnetoresistance (CMR) effect. A good example of these properties is (La_1−2x Pr _x Ca _x )MnO₃ (LPCMO) type CMR material. In this communication it is reported that, with the increase in x (for x=0.1, 0.15, 0.2), the T _c varies between 100 and 120 K with improvisation in metal-insulator transition. Interestingly, resistance increases with x from few hundred ohms to few kilo ohms with corresponding decrease in the unit cell volume. The results of the studies using X-ray diffraction (XRD), electrical resistivity, magnetoresistance and ac susceptibility measurements on LPCMO samples for understanding the structural, transport and magnetic properties are discussed in detail.