Organocatalyzed regioselective and enantioselective synthesis of 1,4- and 1,2-dihydropyridines

Abstract

Herein, we introduce one of the first examples of asymmetric organocatalyzed synthesis of 1,2-dihydropyridines, affording enantioselective access to and partially solving regioselectivity challenges in the synthesis of dihydropyridines. We demonstrate that through modification of organocatalysts both 1,2- and 1,4-dihydropyridines (1,2- and 1,4-DHPs) can be obtained with high regioselectivity (ratio of 1,2-DHP/1,4-DHP from 95/5 to 0/100) and enantioselectivity (33% ee for 1,2-DHPs and up to 98% ee for 1,4-DHPs) in good yields (up to 87%).     

CO Hydrogenation on Cobalt‐Based Catalysts: Tin Poisoning Unravels CO in Hollow Sites as a Main Surface Intermediate

Site poisoning is a powerful method to unravel the nature of active sites or reaction intermediates. The nature of the intermediates involved in the hydrogenation of CO was unraveled by poisoning alumina‐supported cobalt catalysts with various concentrations of tin. The rate of formation of the main reaction products (methane and propylene) was found to be proportional to the concentration of multi‐bonded CO, likely located in hollow sites. The specific rate of decomposition of these species was sufficient to account for the formation of the main products. These hollow‐CO are proposed to be main reaction intermediates in the hydrogenation of CO under the reaction conditions used here, while linear CO are mostly spectators.     

Integrated Si‐based nanoplasmonic sensor with phase‐sensitive angular interrogation

This work is related to the development of an integrated Surface Plasmon Resonance (SPR) sensor on silicon platform. The optical properties of metallic nanogratings fabricated on the semiconductor structure allow direct plasmonic detection in transmission mode. Specially designed angular interrogation method provides a periodic signal with phase dependent on the conditions of surface plasmon excitation. Proposed technique leads to sensitivity better than 10^?6 RIU for conventional SPR Kretschmann configuration and was tested on the integrated Si‐based nanoplasmonic chip. Developed concept is promising for low‐cost mono and multi ‐sensing applications by portable or stationary platforms.     

First syntheses of 2-hydrogeno-2-oxo-1,4,2-oxazaphosphinanes via intramolecular esterification

Synthesis of 2-hydrogeno-2-oxo-1,4,2-oxazaphosphinanes via either intramolecular transesterification, using potassium tert-butylate as catalytic agent, or phosphinic acid esterification, is described for the first time.     

Two-photon absorption in linear bis-dioxaborine compounds-the impact of correlation-induced oscillator-strength redistribution.

Quantum-chemical calculations of the two-photon absorption (TPA) cross-sections are used to determine the characteristics of the electronic excited states responsible for the observed peaks in the TPA spectra of two bis-dioxaborine-substituted biphenyl derivatives. We find two distinct TPA-active states with very different TPA cross-sections: the difference is explained on the basis of electron correlation. These effects, on the one hand, lead to TPA cross-sections of up to 500 x 10(-50) cm4 s photon(-1) for the state favored by correlation; on the other hand, they limit the overall cross-sections achievable in this class of materials.     

Access to functionalized cyclopropylcarbinyl compounds from homoallylic ethers via zirconocene intermediates

Cyclopropylcarbinylzirconium complexes were generated from homoallylic ethers and zirconocene (Cp₂ZrCl₂/2n-BuLi). They underwent further in situ transformations that is, bromination-substitution, transmetallation-functionalization and insertion reactions to afford various cyclopropylcarbinyl derivatives. In contrast, ring-opening products could be selectively obtained by treating the zirconium complex with MeLi, prior to functionalization.     

Photoswitch based on remarkably simple naphthopyrans

Photochromic switches built around 5-carbonyl-3,3-diphenyl-3H-naphtho[2,1-b]pyran unit have been synthesized. Their open forms are constituted of a 1:1 ratio of TC and TT-isomers according to ¹⁹F and ¹H NMR investigations. Electrocyclization of TT isomers back to the closed form is efficiently achieved upon visible irradiation whereas it has been found to be a particularly unfavoured thermal process. These simple 2H-chromenes could act as molecular photoswitch at ambient temperature.     

Template-directed self-organized silica beads on square and Penrose-like patterns

Since a decade photonic band gap research is expanding quickly and especially with self-assembled silica beads, called opals. However, a lot of problems are arising in their preparation, in particular the difficulty to produce large frequencies band gaps in common (periodic) silica photonic materials. To solve this problem quasiperiodic opals are known to be good candidates. Actually, the high degree of isotropy and the high homogeneity of Penrose tilings make them a good way to generate complete photonic band gaps. The aim of our group is to elaborate quasiperiodic photonic crystals by directed-assembly (dip-coating) on Penrose-like patterned surfaces (through electron beam lithography). We will briefly present the different elaboration steps of our opals. Thus, the patterning methods and the dip-coating system will be discussed with our recent results in dip-coated photonic crystals.     

Periodic reiterated homogenization for elliptic functions

In this paper, we study reiterated homogenization for equations of the form . We assume that a is a Carathéodory function and satisfies some monotonicity and growth conditions and its reiterated unfolding converges almost everywhere to a Carathéodory type function. Under these assumptions, we show that the sequence of solutions converges to the solution of a limit variational problem. In particular this contains the case , where a is periodic in the second and third arguments, and continuous in each argument.     

Ueber die Verbrennung der Steinkohle

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