Catalyst‐Free Deaminative Functionalizations of Primary Amines by Photoinduced Single‐Electron Transfer

The use of pyridinium‐activated primary amines as photoactive functional groups for deaminative generation of alkyl radicals under catalyst‐free conditions is described. By taking advantage of the visible light absorptivity of electron donor–acceptor complexes between Katritzky pyridinium salts and either Hantzsch ester or Et₃N, photoinduced single‐electron transfer could be initiated in the absence of a photocatalyst. This general reactivity platform has been applied to deaminative alkylation (Giese), allylation, vinylation, alkynylation, thioetherification, and hydrodeamination reactions. The mild conditions are amenable to a diverse range of primary and secondary alkyl pyridiniums and demonstrate broad functional group tolerance.     

Triphenylphosphine and sodium iodide: a new catalyst combination to rival precious metal complexes in visible light photoredox catalysis

<正>Photoredox catalysis has changed the landscape of modern synthetic organic chemistry by prompting a dramatic increase in research activity into reactions that proceed through free radical intermediates~([1]). Instrumental in this shift in interest from two-electron to single-electron processes was the widespread appreciation of the synthetic utility of pho-     

Solutions with concentration for conservation laws with discontinuous flux and its applications to numerical schemes for hyperbolic systems

Measure-valued weak solutions for conservation laws with discontinuous flux are proposed and explicit formulae have been derived. We propose convergent discontinuous flux-based numerical schemes for the class of hyperbolic systems that admit nonclassical -shocks, by extending the theory of discontinuous flux for nonlinear conservation laws to scalar transport equation with a discontinuous coefficient. The article also discusses the concentration phenomenon of solutions along the line of discontinuity, for scalar transport equations with a discontinuous coefficient. The existence of the solutions for transport equation is shown using the vanishing viscosity approach and the asymptotic behavior of the solutions is also established. The performance of the numerical schemes for both scalar conservation laws and systems to capture the -shocks effectively is displayed through various numerical experiments.     

ortho‐Directing Chromium Arene Complexes as Efficient Mediators for Enantiospecific C(sp2)–C(sp3) Cross‐Coupling Reactions

A new strategy for the coupling of a broad scope of electronically diverse aromatics to boronic esters is reported. The coupling sequence, which relies on the directed ortho‐lithiation of chromium arene complexes followed by boronate formation and oxidation, occurs with complete ortho‐selectivity and enantiospecificity to give the coupling products in excellent yields and with high functional group tolerance. An intermediate chromium arene boronate complex was characterized by X‐ray, NMR, and IR experiments to elucidate the reaction mechanism.     

Wavelength selective materials modification of bulk As2S3 and As2Se3 by free electron laser irradiation

In this study we report first measurements of wavelength-selective infrared-induced materials modification of bulk As₂S₃ and As₂Se₃. These materials are currently being considered as candidate materials for infrared optical fiber transmission in the range of 1–10 μm. Our study is aimed at modifying oxygen, hydrogen and carbon impurities bound to chalcogenide constituent elements in the materials to reduce absorption. Tunable infrared radiation from the W.M. Keck Free Electron Laser (FEL) at Vanderbilt was used to excite specific vibrational modes, S–O–H and CH_x modes in bulk As₂S₃ and Se–H, CH_x and S–H₂ modes in bulk As₂Se₃. Changes in vibrational mode amplitudes are monitored by measuring the intensity of the Fourier transform infrared (FTIR) spectra before and after irradiation at appropriate wavelengths. By tuning wavelengths to hydrogen vibrational modes, we find evidence that hydrogen is released and/or redistributed athermally. In particular, following irradiation at specific resonant wavelengths, vibrational mode amplitudes as monitored by FTIR associated with CH_x are significantly reduced in bulk As₂S₃ and As₂Se₃ samples. In As₂S₃, the changes in CH_x modes are reversed by heat treatment at 115°C for 35 min in nitrogen atmosphere.     

Photoredox-Catalyzed Decarboxylative Bromination,Chlorination and Thiocyanation Using Inorganic Salts

Decarboxylative halogenation reactions of alkyl carboxylic acids are highly valuable reactions for the synthesis of structurally diverse alkyl halides. However, many reported protocols rely on stoichiometric strong oxidants or highly electrophilic halogenating agents. Herein, we describe visible-light photoredox-catalyzed decarboxylative halogenation reactions of N-hydroxyphthalimide-activated carboxylic acids that avoid stoichiometric oxidants and use inexpensive inorganic halide salts as the halogenating agents. Bromination with lithium bromide proceeds under simple, transition-metal-free conditions using an organic photoredox catalyst and no other additives, whereas dual photoredox-copper catalysis is required for chlorination with lithium chloride. The mild conditions display excellent functional-group tolerance, which is demonstrated through the transformation of a diverse range of structurally complex carboxylic acid containing natural products into the corresponding alkyl bromides and chlorides. In addition, we show the generality of the dual photoredox-copper-catalyzed decarboxylative functionalization with inorganic salts by extension to thiocyanation with potassium thiocyanide, which was applied to the synthesis of complex alkyl thiocyanates.     

Regio- and Z-Selective Alkyne Hydroamination and Hydrophenoxylation using Tetrafluoro-λ6-Sulfanyl Alkynes under Superbasic,Naked Anion Conditions

Alkyne hydroamination is an effective approach for the production of enamines and enamine-containing N-heterocycles. However, stereoselectivity control is a considerable challenge in this reaction because of the electronic repulsion between an incoming nitrogen lone pair and the alkyne π-system. Herein, we propose a methodology involving β-regio- and Z-selective alkyne hydroamination by using tetrafluoro-λ⁶-sulfanyl (SF₄) alkynes under superbasic, naked anion conditions. The reaction is compatible with a wide variety of N-heterocycles, including indoles, carbazoles, pyrazoles, and imidazoles, and selectively furnishes SF₄-linked Z-vinyl enamines with β-regioselectively. Moreover, the method can be extended to the β- and Z-controlled, base-mediated alkyne hydrophenoxylation with phenols to provide SF₄-linked Z-vinyl ethers in high yields. As the SF₄ unit has attracted attention as a bioisostere for alkynes, p-benzenes, bicyclo[1.1.1]pentyl (BCP) groups, and cubanes in medicinal chemistry, this chemistry represents an effective approach to creating novel drug candidates incorporating SF₄-containing molecules.     

Trace element determination in thorium oxide using total reflection X-ray fluorescence spectrometry

Applicability of Total Reflection X-ray Fluorescence (TXRF) spectrometry for the determination of trace metals at concentration of µg/g level in thorium oxide was studied. The TXRF spectrometer was calibrated using a multielement standard solution and the method was validated by analyzing another multielement standard solution. Sample preparation conditions were optimized for the TXRF determinations of trace metals in thorium oxide. The elements K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Ba and Pb present in thorium oxide standards were determined after dissolving them in HNO₃/HF mixture and separating the bulk matrix, thorium, by solvent extraction using tri-n-butyl phosphate (TBP) and tri-n-octyl phosphine oxide (TOPO) as extractants. A comparison of TXRF determined concentrations of trace elements Ca, V, Cr, Mn, Fe, Ni and Cu with the certified values shows that TXRF determined concentrations have an RSD of 20% (1 s for n = 4) and are within an agreement of 20% of the certified values in most of the cases.