3-Silanyl-propenylphosphonates: Properties and alkylation potential

Two 3-silanyl-propenylphosphonate esters ( 1a , 1b ) were synthesized, and their deprotonation was attempted using RONa/ROH, RLi/THF, and LDA/THF systems. In the first two cases, the nucleophilic addition was the predominant (or exclusive) reaction observed; deprotonation was achieved with LDA, as confirmed by the reaction of the lithiated species with alkylating agents and with benzaldehyde. Chemical behavior of substrates 1 does not parallel closely that of the parent silanyl or phosphoryl-substituted allylic systems. © John Wiley & Sons, Inc.     

Polyethylene diblock copolymers: Direct synthesis and morphological analysis

Polystyrene and polybutadiene were block copolymerized with high density polyethylene using a transformation reaction from an anionic to a Ziegler-Natta type polymerization. Various reaction parameters were investigated and optimized. Efficiencies of conversion of the anionic block to diblock were as high as 33% (100% normalized) consistent with the known 3/1 Li-R/Ti relationship in the active catalyst species. The activity of the polymeric Li-R/Ti catalyst with regards to ethylene polymerization was as high as 40 000 grams of polymer/mole Ti. Characterization of the resultant polymers is consistent with diblock copolymer structures but transmission electron microscopy shows distinct differences between the morphological behavior of these materials and the now well established morphological behavior of amorphous-amorphous diblock copolymers. These differences are readily explained by consideration of the interactions between the competing thermodynamic processes of microphase separation and crystallization.     

Polymers with indan units

Cationic polymerisation of 1, 4-diisopropenyl benzene, 1, 4-(2-chloro-isopropyl)benzene and related compounds yields soluble polymers with repeating units of indan. High performance polymers with indan units are available via nucleophilic substitution of halogenated aromatic monomers containing a central indan element, which are synthesized from 1, 1, 3-trimethyl-3-phenylindan via Friedel-Crafts-reaction with corresponding halogenated acyl- and sulfonyl chlorides.     

Dual Description of the Superconducting Phase Transition

The dual approach to the Ginzburg-Landau theory of a Bardeen-Cooper-Schrieffer superconductor is reviewed. The dual theory describes a grand canonical ensemble of fluctuating closed magnetic vortices, of arbitrary length and shape, which interact with a massive vector field representing the local magnetic induction. When the critical temperature is approached from below, the magnetic vortices proliferate. This is signaled by the disorder field, which describes the loop gas, developing a non-zero expectation value in the normal conducting phase. It therby breaks a global U(1) symmetry. The ensuing Goldstone field is the magnetic scalar potential. The superconducting-to-normal phase transition is studied by applying renormalization group theory to the dual formulation. In the regime of a second-order transition, the critical exponents are given by those of a superfluid with a reversed temperature axis.     

Complexes of tricoordinate hypervalent pnictogens with pentamethylcyclopentadienylruthenium

The complexes of a pentamethylcyclopentadienylruthenium moiety with hypervalent tricoordinate pnictogens are reported. A unique mode of complexation is observed for each of the different pnictogens (P, As, Sb). The phosphorus derived complex exhibits an 8-electron tetrahedral bonding environment at phosphorus. The antimony derived complex maintains a 10-electron bonding system at antimony with a pseudo-trigonalbipyramidal geometry at antimony. The arsenic-containing complex is formed with destruction of the original arsenic heterocycle and formation of a trinuclear Ru–Ru–As ring. Remarkably, the formation of the arsenic ruthenium complex can be reversed to reconstruct the original arsenic heterocycle.     

Alkaloids and Colon Cancer: Molecular Mechanisms and Therapeutic Implications for Cell Cycle Arrest

Cancer is the second most fatal disease worldwide, with colon cancer being the third most prevalent and fatal form of cancer in several Western countries. The risk of acquisition of resistance to chemotherapy remains a significant hurdle in the management of various types of cancer, especially colon cancer. Therefore, it is essential to develop alternative treatment modalities. Naturally occurring alkaloids have been shown to regulate various mechanistic pathways linked to cell proliferation, cell cycle, and metastasis. This review aims to shed light on the potential of alkaloids as anti-colon-cancer chemotherapy agents that can modulate or arrest the cell cycle. Preclinical investigated alkaloids have shown anti-colon cancer activities and inhibition of cancer cell proliferation via cell cycle arrest at different stages, suggesting that alkaloids may have the potential to act as anticancer molecules.     

Stereoretentive and regioselective selenium-catalyzed intermolecular propargylic C–H amination of alkynes

Herein we report an intermolecular propargylic C–H amination of alkynes. This reaction is operationally convenient and requires no transition metal catalysts or additives. Terminal, silyl, and internal alkynes bearing a wide range of functional groups can be aminated in high yields. The regioselectivity of amination for unsymmetrical internal alkynes is strongly influenced by substitution pattern (tertiary > secondary > primary) and by relatively remote heteroatomic substituents. We demonstrate that amination of alkynes bearing α-stereocenters occurs with retention of configuration at the newly-formed C–N bond. Competition experiments between alkynes, kinetic isotope effects, and DFT calculations are performed to confirm the mechanistic hypothesis that initial ene reaction of a selenium bis(imide) species is the rate- and product-determining step. This ene reaction has a transition state that results in substantial partial positive charge development at the carbon atom closer to the amination position. Inductive and/or hyperconjugative stabilization or destabilization of this positive charge explains the observed regioselectivities.

Selenium catalysis enables a general intermolecular propargylic C–H amination of alkynes. The concerted mechanism gives rise to high regioselectivity for the more electron-rich end of the alkyne and retention of the C–H propargylic stereocenter.