Controlled Reduction of Carboxamides to Alcohols or Amines by Zinc Hydrides

New protocols for controlled reduction of carboxamides to either alcohols or amines were established using a combination of sodium hydride (NaH) and zinc halides (ZnX₂). Use of a different halide on ZnX₂ dictates the selectivity, wherein the NaH‐ZnI₂ system delivers alcohols and NaH‐ZnCl₂ gives amines. Extensive mechanistic studies by experimental and theoretical approaches imply that polymeric zinc hydride (ZnH₂)_∞ is responsible for alcohol formation, whereas dimeric zinc chloride hydride (H?Zn?Cl)₂ is the key species for the production of amines.     

Radical polymerization of trifluoromethyl‐substituted methyl methacrylates and their application for use in pressure‐sensitive paint

Three CF₃‐substituted methyl methacrylates (MMAs), 2,2,2‐trifluoroethyl methacrylate (TFEMA), 1,1,1,3,3,3‐hexafluoroisopropyl methacrylate (HFIPMA) and nonafluoro‐tert‐butyl methacrylate (NFTBMA), were polymerized by conventional radical polymerization to give oxygen‐permeable polymers for application in pressure‐sensitive paint (PSP). The radical copolymerizations of styrene with TFEMA, HFIPMA, or NFTBMA were carried out to examine the effect of CF₃ groups on the polymerizability. The e values increased in the order of MMA (0.40) < TFEMA (0.76) < HFIPMA (1.19) < NFTBMA (1.31). The homopolymers of TFEMA, HFIPMA and NFTBMA (PTFEMA, PHFIPMA, and PNFTBM, respectively) were examined as polymers for use in PSP using 5,10,15,20‐tetrakis(pentafluorophenyl)porphinato platinum(II) (PtTFPP). The PSP consisting of PNFTBMA and PtTFPP exerted very high pressure sensitivity and very low temperature sensitivity. In the absence of oxygen, the temperature sensitivity decreased in the order of PTFEMA > PHFIPMA > PNFTBMA = PMMA, which corresponds to the order of glass transition temperatures (T_g). However, the activation energies of the overall process of the luminescence quenching by oxygen were found to be 16.8 (PMMA), 13.0 (PTFEMA), 6.8 (PHFIPMA), and 4.3 kJ mol^?1 (PNFTBMA). Therefore, the low temperature sensitivity of PNFTBMA was attributed to its high degree of substitution with CF₃ groups and to its relatively high T_g value. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 963–972     

Polymerization-induced self-assembly of amino-acid-based nano-objects by reversible addition–fragmentation chain-transfer dispersion polymerization

A series of amino-acid-based amphiphilic diblock copolymer nano-objects having different morphologies were developed by reversible addition–fragmentation chain-transfer (RAFT) dispersion polymerization of styrene (St) in methanol. This was mediated by six different hydrophilic poly(N-acryloyl amino acid) macro-chain transfer agents (CTAs), including three carboxylic-acid-containing ones, poly(N-acryloyl-l -proline) (PAProOH), poly(N-acryloyl-4-trans-hydroxy-l -proline) (PAHypOH), and poly(N-acryloyl-l -threonine) (PAThrOH) prepared by RAFT polymerization, and their methyl ester forms, PAProOMe, PAHypOMe, and PAThrOMe. The effects of polymerization conditions on RAFT dispersion polymerization of St using a dithiocarbamate-terminated PAProOH was investigated. A systematic study of the effects of monomer conversion and concentration afforded the formation of various morphologies (i.e., spheres, worms, and vesicles). The effects of hydrogen-bonding and ionic interactions of the macro-CTAs on the assembled structures of the nano-objects were evaluated using six different macro-CTAs. Transforming the products from methanol to water via dialysis produced amino-acid-based block copolymer nano-objects, exhibiting pH-responsive morphological change, in aqueous solution.     

Induced Production,Synthesis, and Immunomodulatory Action of Clostrisulfone,a Diarylsulfone from Clostridium acetobutylicum

The anaerobe Clostridium acetobutylicum belongs to the most important industrially used bacteria. Whereas genome mining points to a high potential for secondary metabolism in C. acetobutylicum, the functions of most biosynthetic gene clusters are cryptic. We report that the addition of supra-physiological concentrations of cysteine triggered the formation of a novel natural product, clostrisulfone ( 1 ). Its structure was fully elucidated by NMR, MS and the chemical synthesis of a reference compound. Clostrisulfone is the first reported natural product with a diphenylsulfone scaffold. A biomimetic synthesis suggests that pentamethylchromanol-derived radicals capture sulfur dioxide to form 1 . In a cell-based assay using murine macrophages a biphasic and dose-dependent regulation of the LPS-induced release of nitric oxide was observed in the presence of 1 .     

Control of Axial Chirality by Planar Chirality Based on Optically Active [2.2]Paracyclophane

Optically active X-shaped molecules based on the planar chiral [2.2]paracyclophane building block were prepared, in which di(methoxy)terphenyl units were stacked on the central benzene rings. At 25 °C, anisolyl rings freely rotate in solution, while in the crystal form, they are fixed by intramolecular CH–π interactions, thereby leading to the expression of the axial chirality, i.e., propeller chirality was exhibited by the planar chiral [2.2]paracyclophane moiety. The X-shaped molecule exhibited good circularly polarized luminescence (CPL) profiles with moderate Φ_PL and a large g_lum value in the order of 10⁻³ at 25 °C, in solution. In contrast, at −120 °C, dual CPL emission with opposite signs was observed. According to the theoretical studies, the rotary motion of the anisolyl units is suppressed in the excited states, and so emission from two isomers could be observed. These results demonstrate that the axial chirality was controlled by the planar chirality, leading ultimately to propeller chirality.     

Rhodium-Catalyzed ortho-Bromination of O-Phenyl Carbamates Accelerated by a Secondary Amide-Pendant Cyclopentadienyl Ligand

It has been established that a newly developed cyclopentadienyl rhodium(III) [Cp^ARh^III] complex, bearing an acidic secondary amide moiety on the Cp ring, is able to catalyze the ortho-bromination of O-phenyl carbamates with N-bromosuccinimide (NBS) at room temperature. The presence of the acidic secondary amide moiety on the Cp^A ligand accelerates the bromination by the hydrogen bond between the acidic NH group of the Cp^A ligand and the carbonyl group of NBS.     

The resonant secondary emission of the F center in alkali halides

The secondary radiation after resonant excitation of F center and its linear polarization P correlated to the polarization of resonant light have been measured for five alkali halides at low temperatures. In KC1, the spectrum of P over the whole Stokes region is divided into three successive regions, the depolarization range at the one-phonon Raman scattering, the near plateau range, and the depolarization range down to vanishing. The former two have common relevance to resonant energy and symmetries of coupled phonons. These relevances are interpreted adopting a configuration coordinate model for 2s- and 2p-like excited states.