Copper-Photocatalyzed Hydrosilylation of Alkynes and Alkenes under Continuous Flow

Herein, the photocatalytic hydrosilylation of alkynes and alkenes under continuous flow conditions is described. By using 0.2 mol % of the developed [Cu(dmp)(XantphosTEPD)]PF₆ under blue LEDs irradiation, a large panel of alkenes and alkynes was hydrosilylated in good to excellent yields with a large functional group tolerance. The mechanism of the reaction was studied, and a plausible scenario was suggested.     

Copper-Photocatalyzed Borylation of Organic Halides under Batch and Continuous-Flow Conditions

The copper-photocatalyzed borylation of aryl, heteroaryl, vinyl and alkyl halides (I and Br) was reported. The reaction proceeded using a new heteroleptic Cu complex under irradiation with blue LEDs, giving the corresponding boronic-acid esters in good to excellent yields. The reaction was extended to continuous-flow conditions to allow an easy scale-up. The mechanism of the reaction was studied and a mechanism based on a reductive quenching (Cu^I/Cu^I*/Cu⁰) was suggested.     

A De Giorgi–Type Conjecture for Minimal Solutions to a Nonlinear Stokes Equation

We study the one-dimensional symmetry of solutions to the nonlinear Stokes equation which are periodic in the d − 1 last variables (living on the torus 𝕋^d−1) and globally minimize the corresponding energy in Ω = ℝ × 𝕋^d−1, i.e., Namely, we find a class of nonlinear potentials W ≥ 0 such that any global minimizer u of E connecting two zeros of W as x₁ → ± ∞ is one-dimensional; i.e., u depends only on the x₁ -variable. In particular, this class includes in dimension d = 2 the nonlinearities with w being a harmonic function or a solution to the wave equation, while in dimension d ≥ 3 , this class contains a perturbation of the Ginzburg-Landau potential as well as potentials W having d + 1 wells with prescribed transition cost between the wells. For that, we develop a theory of calibrations relying on the notion of entropy (coming from scalar conservation laws). We also study the problem of the existence of global minimizers of E for general potentials W providing in particular compactness results for uniformly finite energy maps u in Ω connecting two wells of W as x₁ → ± ∞ . © 2019 Wiley Periodicals, Inc.     

Photocatalytic E→Z Contra-Thermodynamic Isomerization of Vinyl Silanes with Lewis Base

Herein, we disclosed the contra-thermodynamic E→Z isomerization of alkenyl silanes, according to the in situ formation of a chromophoric species, in the presence of rac-BINAP as the catalyst. The reaction carried out in DMSO or CH₃CN under irradiation at 405 nm allowed the interconversion of the E-isomers into the Z-congeners in good to excellent yields and outstanding Z/E selectivities, on 18 examples. Finally, the mechanism of this E→Z isomerization was studied to get insight into the reaction mechanism.     

Recent Progress in Direct Introduction of Fluorinated Groups on Alkenes and Alkynes by means of CH Bond Functionalization

The direct introduction of fluorine and fluorinated building blocks has recently attracted a lot of attention and particularly the direct functionalization of alkenes and alkynes. This review will highlight the major progress recently made in that field, with a focus on photocatalyzed transformations, base‐promoted processes, and transition metal‐catalyzed functionalization of alkenes and alkynes. Special attention will be paid to explanations of the reaction mechanisms.     

Image recovery via total variation minimization and related problems

Summary. We study here a classical image denoising technique introduced by L. Rudin and S. Osher a few years ago, namely the constrained minimization of the total variation (TV) of the image. First, we give results of existence and uniqueness and prove the link between the constrained minimization problem and the minimization of an associated Lagrangian functional. Then we describe a relaxation method for computing the solution, and give a proof of convergence. After this, we explain why the TV-based model is well suited to the recovery of some images and not of others. We eventually propose an alternative approach whose purpose is to handle the minimization of the minimum of several convex functionals. We propose for instance a variant of the original TV minimization problem that handles correctly some situations where TV fails. Received December 21, 1995 / Revised version February 26, 1996     

Photoelectron imaging of helium droplets

The photoionization and photoelectron spectroscopy of He nanodroplets (10(4) atoms) has been studied by photoelectron imaging with photon energies from 22.5-24.5 eV. Total electron yield measurements reveal broad features, whose onset is approximately 1.5 eV below the ionization potential of atomic He. The photoelectron spectra are dominated by very low energy electrons, with less than 0.6 meV. These results are attributed to the formation and autoionization of highly vibrationally excited He(*)(n) Rydberg states within the cluster, followed by strong final state interactions between the photoelectron and the droplet.