Atropoenantioselective palladaelectro-catalyzed anilide C–H olefinations viable with natural sunlight as sustainable power source

Enantioselective electrocatalyzed transformations represent a major challenge. We herein achieved atropoenantioselective pallada-electrocatalyzed C–H olefinations and C–H allylations with high efficacy and enantioselectivity under exceedingly mild reaction conditions. With (S)-5-oxoproline as the chiral ligand, activated and non-activated olefins were suitable substrates for the electro-C–H activations. Dual catalysis was devised in terms of electro-C–H olefination, along with catalytic hydrogenation. Challenging enantiomerically-enriched chiral anilide scaffolds were thereby obtained with high levels of enantio-control in the absence of toxic and cost-intensive silver salts. The resource-economy of the transformation was even improved by directly employing renewable solar energy.

Asymmetric pallada-electrocatalyzed C–H activation of achiral anilides were accomplished by catalyst control with high levels of enantioselectivity. Dual catalysis was devised, while photovoltaic cells could be used to empower the electrocatalysis.     

1λ5,3λ5-Diphospholium ions

One example each is given for the reaction of bromoacetylenes and ethynyl-phenyliodonium tosylates with bis(diphenyl phosphino)methane. The yellow crystalline 1:1-addition products are diphospholium salts. They readily and selectively hydrolyze to give 2-phosphinoylethenyl phosphonium salts.     

Yrast level structure of the neutron-deficient N = 80 isotones 146Dy, 147Ho and 148Er up to high-spin values

High-spin level schemes of the N = 80 isotones ¹⁴⁶Dy, ¹⁴⁷Ho and ¹⁴⁸Er have been investigated by in-beam γ-ray spectroscopic methods using the NORDBALL Compton-suppressed multidetector array including proton and neutron selection. The projectile-target system ⁵⁸Ni + ⁹²Mo at 260 MeV beam energy has been used to produce the neutron-deficient N = 80 isotones. The previously known schemes have been extended to considerably higher spin and exitation energy, up to I = 23?, E _x≈ 8.9 MeV in ¹⁴⁶Dy, I = 53/2?, E _x≈ 8.7 MeV in ¹⁴⁷Ho and I = 23?, E _x≈ 9.6 MeV in ¹⁴⁸Er. The results are discussed in terms of the spherical shell model. Many of the levels can be described within this framework. Received: 12 January 2001 / Accepted: 11 April 2001     

Modification of the physical properties of polymers by supramolecular interactions

Using molecular recognition, receptors based upon diphenylglycoluril have been clipped onto paraquat polymers and styrene copolymers. In the case of the former polymers, the viscosity and electrochemical behaviour was modified. In the case of the latter, liquid crystallinity was induced upon complexation.     

Production of Polyacrylic Acid Homo- and Copolymer Films by Electrochemically Induced Free-Radical Polymerization: Preparation and Swelling Behavior

Films of polyacrylic acid hydrogels were produced on a conducting substrate by means of electrochemically initiated polymerization (EIP). An electro-chemical quartz crystal microbalance was used to monitor film growth in situ. Homopolymer and copolymer films of polyacrylic acid and poly-N-isopropylacrylamide were characterized by FTIR spectroscopy. The degree of swelling of these films could be tuned via the pH.     

Particle hole yrast states in146Gd and147Gd and the Z=64 shell closure

The level structures of¹⁴⁶Gd and¹⁴⁷Gd have been investigated by in-beamγ-ray ande ^? spectroscopy with (α, xn) reactions on enriched Sm targets. Detailed level schemes up to ～4 MeV, which differ radically from earlier schemes, are reported. The energy levels are characterized as particle-hole excitations using empirical single particle energies and two nucleon interactions. Analysis of pure 1p 1h proton excitations demonstrates that theZ=64 andN=82 energy gaps are about equally large.     

Kinetics of reactions between methoxycarbonyl,methyl, and methoxy radicals formed in flash photolysis of dimethyl oxalate in gas phase

Flash photolysis of dimethyl oxalate produced the radicals CH₃, CH₃O, and COOCH₃. Thermally equilibrated methoxycarbonyl radicals did not decompose during radicalradical reactions in the presence of 40-torr cyclohexane in the temperature range 298–448 K. Cyclohexyl radicals were also generated during the flash photolysis of the reaction mixture. Rate coefficients of radical–radical reactions were calculated from the amounts of stable products determined by gas chromatography: CO, CO₂, CH₄, C₂H₄, C₂H₆, CH₂O, CH₃OH, CH₃OCH₃, HCOOCH₃, CH₃COOCH₃, CH₃OCOOCH₃, CH₃C₆H₁₁, and CH₃OC₆H₁₁. Calculations were performed using an iterative computer integration program. Absolute values of rate coefficients were based on the rate coefficient of the reaction between methyl radicals, k₁ = 2.7 × 10¹⁰ dm³ mol^?1 s^?1, measured with the same equipment. The rate coefficients for reactions (5)–(8) are:      

The two particle-phonon multiplet πh 11/2 νf 7/2 × 3− and higher-lying four-nucleon yrast states in the doubly-odd nucleus 146 63 Eu83

The isotopes¹⁵B,¹⁸C,^19,20N,^34,35Al and³⁹P have been produced as projectile-like fragments from the interaction of a⁸⁶Kr beam of 45 MeV/u from GANIL with a¹⁸¹Ta target. Separated by the 0° magnetic analyser LISE, the nuclei are identified by means of aΔE- E semiconductor telescope. It is surrounded, in a geometry close to 4π, by a thin plastic scintillator (NE 102) and a large volume liquid scintillator (NE 213) for the detection of betas and neutrons, respectively, from the decay of the implanted nuclei. By observation of theβ-delayed neutrons, the half-livesT _1/2 and neutron emission probabilitiesP _n have been measured. TheT _1/2 of¹⁸C,²⁰N,³⁵Al,³⁹P and P_n of¹⁸C,^19,20N,^34,35Al and³⁹P are determined for the first time. For the isotopes¹⁷C,^36,37Si and³⁸P upper limits of P_n are deduced.