Shifting From Ziegler–Natta to Philips‐Type Catalyst? A Simple and Safe Access to Reduced Titanium Systems for Ethylene Polymerization

Silica‐supported titanium(IV) chloride is readily reduced by Mashima and co‐workers' reagent (1‐methyl‐3,6‐bis(trimethylsilyl)‐1,4‐cyclohexadiene) to afford materials active in ethylene polymerisation without need of aluminum alkyl cocatalyst.     

Effective algebraic degeneracy

We show that for every smooth projective hypersurface X⊂ℙ ⁿ⁺¹ of degree d and of arbitrary dimension n ≥2, if X is generic, then there exists a proper algebraic subvariety Y ⊊ X such that every nonconstant entire holomorphic curve f :ℂ→X has image f(ℂ) which lies in Y, as soon as its degree satisfies the effective lower bound d\geqslant 2ⁿ⁵d\geqslant 2^{n^{5}} .     

Comportement asymptotique à haute conductivité de l'épaisseur de peau en électromagnétisme

We study a three-dimensional model for the skin effect in electromagnetism. We first give a multiscale asymptotic expansion for the solution of the harmonic Maxwell equations set on a domain made of two materials, dielectric and highly conducting, with a regular interface between them. To measure the skin effect, we introduce a suitable skin depth function defined on the interface and generalizing the classical scalar quantity. We then prove an asymptotic expansion at high conductivity for this function, which exhibits the influence of the geometry of the interface on the skin depth.     

Bioinspired Oxidative Cyclization of the Geissoschizine Skeleton for Enantioselective Total Synthesis of Mavacuran Alkaloids

Reported is the enantioselective total syntheses of mavacuran alkaloids, (+)‐taberdivarine H, (+)‐16‐hydroxymethyl‐pleiocarpamine, and (+)‐16‐epi‐pleiocarpamine, and their postulated biosynthetic precursor 16‐formyl‐pleiocarpamine. This family of monoterpene indole alkaloids is a target of choice since some of its members are subunits of intricate bisindole alkaloids such as bipleiophylline. Inspired by the biosynthetic hypothesis, an oxidative coupling approach from the geissoschizine framework to form the N1?C16 bond was explored. Quaternization of the aliphatic nitrogen center was key to achieving the oxidative coupling induced by KHMDS/I₂ as it masks the nucleophilicity of the aliphatic nitrogen center and locks in the required cis conformation.     

Decarboxylative Mannich Reactions with N-Alkyl Imines

The use of N-alkyl imines in decarboxylative Mannich reaction with substituted malonic acids half oxyesters (SMAHOs) has been developed to afford a direct access to secondary β^2,3-aminoesters. The transformation occurs under very practical conditions (DABCO as a catalyst in bulk toluene and open to air) and can be performed with a broad range of each substrate in yields of 36 to 97 %. Importantly, the reaction was found to require the use of acidic additives in combination with the organocatalyst to limit the competitive olefination reaction.     

Synthesis and Thermophysical Properties of Ether‐Functionalized Sulfonium Ionic Liquids as Potential Electrolytes for Electrochemical Applications

During this work, a novel series of hydrophobic room temperature ionic liquids (ILs) based on five ether functionalized sulfonium cations bearing the bis{(trifluoromethyl)sulfonyl}imide, [NTf₂]^? anion were synthesized and characterized. Their physicochemical properties, such as density, viscosity and ionic conductivity, electrochemical window, along with thermal properties including phase transition behavior and decomposition temperature, have been measured. All of these ILs showed large liquid range temperature, low viscosity, and good conductivity. Additionally, by combining DFT calculations along with electrochemical characterization it appears that these novel ILs show good electrochemical stability windows, suitable for the potential application as electrolyte materials in electrochemical energy storage devices.     

Pencils of quadrics and Gromov–Witten–Welschinger invariants of $$\mathbb {C}P^3$$

We establish a formula for the Gromov–Witten–Welschinger invariants of \(\mathbb {C}P^3\) with mixed real and conjugate point constraints. The method is based on a suggestion by J. Kollár that, considering pencils of quadrics, some real and complex enumerative invariants of \(\mathbb {C}P^3\) could be computed in terms of enumerative invariants of \(\mathbb {C}P^1\times \mathbb {C}P^1\) and of elliptic curves.     

Biogenetic hypothesis and first steps towards a biomimetic synthesis of haouamines

A detailed hypothesis for the biogenesis of haouamines is reported herein, supported by experiments headed towards biomimetic synthesis of these compounds.