Mechanical C−C Bond Formation by Laser Driven Shock Wave

Mechanically induced C−C bond formation was demonstrated by the laser driven shock wave generated in liquid normal alkanes at room temperature. Gas chromatography mass spectrometry analysis revealed the dehydrogenation condensation between two alkane molecules, for seven normal alkanes from pentane to undecane. Major products were identified to be linear and branched alkane molecules with double the number of carbons, and exactly coincided with the molecules predicted by supposing that a C−C bond was formed between two starting molecules. The production of the alkane molecules showed that the C−C bond formation occurred almost evenly at all the carbon positions. The dependence of the production on the laser pulse energy clearly indicated that the process was attributed to the shock wave. The C−C bond formation observed was not a conventional passive chemical reaction but an unprecedented active reaction.     

Identifying the Types and Characterization of the Active Sites on M−X−C Single-Atom Catalysts

Single atom catalysts (SACs) have attracted much attention in recent years. As an essential group in SACs, M−X−C (X=nonmetallic element) materials have been demonstrated to be efficient in many reactions. However, identifying the active sites on M−X−C, especially under working conditions, is still challenging, which is crucial for chemists to further understand the mechanism underlying the reaction and better design proper SACs for specific reactions. Herein, the types and characterization of M−X−C are comprehensively summarized and discussed in this review. In addition to the basic information above, the challenges and opportunities remaining in this field will be also proposed to present a perspective to the research on the next step.     

Computational Insights of Selective Intramolecular O-atom Transfer Mediated by Bioinspired Copper Complexes

The stereoselective copper-mediated hydroxylation of intramolecular C−H bonds from tridentate ligands is reinvestigated using DFT calculations. The computational study aims at deciphering the mechanism of C−H hydroxylation obtained after reaction of Cu(I) precursors with dioxygen, using ligands bearing either activated ( L¹ ) or non-activated ( L² ) C−H bonds. Configurational analysis allows rationalization of the experimentally observed regio- and stereoselectivity. The computed mechanism involves the formation of a side-on peroxide species ( P ) in equilibrium with the key intermediate bis-(μ-oxo) isomer ( O ) responsible for the C−H activation step. The P/O equilibrium yields the same activation barrier for the two complexes. However, the main difference between the two model complexes is observed during the C−H activation step, where the complex bearing the non-activated C−H bonds yields a higher energy barrier, accounting for the experimental lack of reactivity of this complex under those conditions.     

Programmed Multiple C-H Bond Functionalization of the Privileged 4-hydroxyquinoline Template

The introduction of substituents on bare heterocyclic scaffolds can selectively be achieved by directed C−H functionalization. However, such methods have only occasionally been used, in an iterative manner, to decorate various positions of a medicinal scaffold to build chemical libraries. We herein report the multiple, site selective, metal-catalyzed C−H functionalization of a “programmed” 4-hydroxyquinoline. This medicinally privileged template indeed possesses multiple reactive sites for diversity-oriented functionalization, of which four were targeted. The C-2 and C-8 decorations were directed by an N-oxide, before taking benefit of an O-carbamoyl protection at C-4 to perform a Fries rearrangement and install a carboxamide at C-3. This also released the carbonyl group of 4-quinolones, the ultimate directing group to functionalize position 5. Our study highlights the power of multiple C−H functionalization to generate diversity in a biologically relevant library, after showing its strong antimalarial potential.     

Synthesis of [5,6]-Bicyclic Heterocycles with a Ring-Junction Nitrogen Atom: Rhodium(III)-Catalyzed C−H Functionalization of Alkenyl Azoles

The first syntheses of privileged [5,6]-bicyclic heterocycles, with ring-junction nitrogen atoms, by transition metal catalyzed C−H functionalization of C-alkenyl azoles is disclosed. Several reactions are applied to alkenyl imidazoles, pyrazoles, and triazoles to provide products with nitrogen incorporated at different sites. Alkyne and diazoketone coupling partners give azolopyridines with various substitution patterns. In addition, 1,4,2-dioxazolone coupling partners yield azolopyrimidines. Furthermore, the mechanisms for the reactions are discussed and the utility of the developed approach is demonstrated by iterative application of C−H functionalization for the rapid synthesis of a patented drug candidate.     

Hemin-Promoted Direct C−H Thiolation in the Synthesis of Diaryl Sulfides

Diaryl sulfides are a class of important synthetic chemical units. Herein, we report a new method for direct preparation of diphenyl sulfides using P-toluenesulfonyl chloride as an effective thiophenyl radical precursor with assistance from Hemin. Various substituted anisoles and benzenesulfonyl chlorides are well tolerated, resulting in moderate to good yields of diaryl sulfides. The potential of the proposed method is validated by good yields obtained in gram scale reactions.     

An ultra-wideband coding polarizer for beam control and RCS reduction

Pancharatnam−Berry (PB) phase metasurface, as a special class of gradient metasurfaces, has been paid much attention owing to the robust performance for phase control of circularly polarized waves. Herein, we present an element-based polarizer for the first step, which enables the incident electromagnetic waves into the cross-polarized waves with the relative bandwidth of 71%, and the polarization conversion ratio exceeds 90% at 6.9−14.5 GHz. Then an eight-elements coding polarizer based on the PB phase is presented for the applications on beam control and radar cross section reduction. The simulated values indicate that the reduction of radar cross section is more than 10 dB at 6−16 GHz. Our work reveals the availability of manipulating the waves, beamforming in communication systems and electromagnetic stealth, and so on.     

Approximation properties of the generalized Szasz operators by multiple Appell polynomials via power summability method

In this paper some properties of the generalized Szasz operators by multiple Appell polynomials are given, using into consideration the power summability method. In the first section are given some direct estimation related to the generalized Szasz operators by multiple Appell polynomials, including Korovkin type theorem. In the second section, we give some results related to the weighted spaces of continuous functions and Voronovskaya type theorem. In the third section, we have proved some results related to the statistical convergence of the generalized Szasz operators by multiple Appell polynomials, using into consideration the A− transformation. At the end of the paper are given some illustrative computational examples which make such summability methods (for example, power series method) more useful and fruitful for applications of functional analysis in approximation theory.     

Synthesis of cyanoalkyl indolines through cyanoalkylarylation of N-allyl anilines with alkyl nitriles under metal-free and neutral conditions

An α-C(sp³)−H functionalization of alkyl nitriles under metal-free and neutral conditions is presented. In the presence of di-tert-butyl peroxide (DTBP), N-allyl anilines underwent exo-selective cyanoalkylation/cyclization cascade, providing a direct access to 3-cyanoalkyl indolines. Previously, a transition-metal catalyst and/or a strong base were generally required to activate nitrilic α-C−H bonds. This reaction features a broad substrate scope and low cost, and primary, secondary and tertiary indolin-3-yl nitriles could all be assembled.     

Intramolecular Ullmann-type C−N coupling for the synthesis of substituted benzo[4,5]imidazo[1,2-a]pyrrolo[3,4-c]pyridines

An efficient CuI catalyzed intramolecular Ullmann-type C−N coupling reaction is described here. Newly substituted 1H-benzo[4,5]imidazo[1,2-a]pyrrolo[3,4-c]pyridine-1,3,5(2H, 11H)-trione has been easily synthesized from ortho halogenated N-substituted pyrrolo[3,4-c]pyridine-1,3,6(5H)-triones in presence of CuI catalyst and K₂CO₃ base without any ligand. This procedure is based on intramolecular Ullmann-type reaction and provides a proficient method of making fused tetracyclic heterocycles.