One-Pot anti-Michael Regio- and Stereoselective Hydroamination of Activated -Allenamides.

-Allenamides, substituted by an ester at the γ-position, were obtained through addition of terminal ynamides with ethyl diazoacetate under copper catalysis for the first time. Regio- and stereoselective hydroamination of those activated -allenamides provided exclusively -configured captodative enamimes through a one-pot anti-Michael addition. Numerous ynamides as well as various secondary amines were adapted in this process.

Copper-Catalyzed Synthesis of Terminal vs. Fluorine-Substituted N-Allenamides via Addition of Diazo Compounds to Terminal Ynamides.

A copper-mediated coupling reaction between ynamides and diazo-compounds to produce N-allenamides is reported for the first time. This method enables facile and rapid access to terminal N-allenamides by using commercially available TMS-diazomethane with wide functional group compatibility on the nitrogen. Furthermore, the ubiquity of molecules containing a fluorine moiety in medicine, in agricultural, and material science requires the continuous search of new building blocks, including this unique surrogate.

Macrolactonization Reactions Driven by a Pentafluorobenzoyl Group*.

Macrolactones constitute a privileged class of natural and synthetic products with a broad range of applications in the fine chemicals and pharmaceutical industry. Despite all the progress made towards their synthesis, notably from seco-acids, a macrolactonization promoter system that is effective, selective, flexible, readily available, and, insofar as possible, compatible with manifold functional groups is still lacking. Herein, we describe a strategy that relies on the formation of a mixed anhydride incorporating a pentafluorophenyl group which, due to its high electronic activation enables a convenient access to macrolactones, macrodiolides and esters with a broad versatility.

Direct Synthesis of CFH-Substituted 2-Amidofurans via Copper-Catalyzed Addition of Difluorinated Diazoacetone to Ynamides.

The significance of molecules containing difluoromethyl groups is driven by their potential applications in pharmaceutical and agrochemical science. Methods for the incorporation of lightly fluorinated groups such as CFH have been less well developed. Here we report the use of difluorinated diazoacetone as a practical reagent for the direct synthesis of CFH-substituted 2-amidofurans through addition to ynamides.

Metal-Free Deoxygenation of Amine N-Oxides: Synthetic and Mechanistic Studies.

We report herein an unprecedented combination of light and P(III)/P(V) redox cycling for the efficient deoxygenation of aromatic amine N-oxides. Moreover, we discovered that a large variety of aliphatic amine N-oxides can easily be deoxygenated by using only phenylsilane. These practically simple approaches proceed well under metal-free conditions, tolerate many functionalities and are highly chemoselective.

Mechanochromic LLDPE Films Doped with NIR Reflective Paliogen Black.

The perylene bisimide derivative Paliogen Black (P-black) is proposed as a new chromogenic probe that shows visible (vis) and near-infrared (NIR) responses after mechanical solicitations of host linear low-density polyethylene (LLDPE) films. P-black is reported to display strong absorption in the vis spectrum and unusual reflective and cooling features in the NIR region. Uniaxial deformation of the 2.

Silver(I) Oxide-/DBU-Promoted Synthesis of Dihydrofuran Units through Allenyl Silver Formation.

A formal [3+2] cyclization mediated by silver(I) oxide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is described herein.

General Density-Based Index to Analyze Charge Transfer Phenomena: From Models to Butterfly Molecules.

We present a new formula and implementation for a descriptor enabling quantification of the electron-hole distance associated with a charge transfer of an optical transition, on the basis of the knowledge of the densities of the electronic ground and excited states. This index is able to define a charge-transfer length even for systems that would be otherwise difficult to treat, like symmetric molecules, while maintaining a very low computational cost and the possibility to be coupled to any method providing ground and excited state electron densities. After a benchmark of its performance on a series of push-pull molecules, the index has been applied to a set of large symmetric luminophores, the so-called "butterfly molecules", showing promising applications in optoelectronics, to highlight its potential use in the design of new compounds.